EP1740623A1 - Polyethylen und katalysatorzusammensetzung für seine herstellung - Google Patents

Polyethylen und katalysatorzusammensetzung für seine herstellung

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Publication number
EP1740623A1
EP1740623A1 EP05750312A EP05750312A EP1740623A1 EP 1740623 A1 EP1740623 A1 EP 1740623A1 EP 05750312 A EP05750312 A EP 05750312A EP 05750312 A EP05750312 A EP 05750312A EP 1740623 A1 EP1740623 A1 EP 1740623A1
Authority
EP
European Patent Office
Prior art keywords
polyethylene
carbon atoms
radicals
alkyl
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05750312A
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English (en)
French (fr)
Other versions
EP1740623B1 (de
Inventor
Jennifer Kipke
Shahram Mihan
Rainer Karer
Dieter Lilge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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Application filed by Basell Polyolefine GmbH filed Critical Basell Polyolefine GmbH
Priority to EP10011158.2A priority Critical patent/EP2322565A3/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1345—Single layer [continuous layer]

Definitions

  • the present invention relates to a novel polyethylene, a catalyst composition and a process for its preparation, and also to fibers, moldings, films or polymer mixtures in which this polyethylene is present.
  • Stress crack formation in plastics is a physicochemical process which does not change the polymer molecules. It is caused, inter alia, by gradual yielding or untangling of the connecting molecular chains. Stress crack formation occurs less readily the higher the mean molecular weight, the broader the molecular weight distribution and the higher the degree of molecular branching, i.e. the lower the densities. It occurs less readily the longer the side chains themselves.
  • Surface-active substances, in particular soaps, and thermal stress accelerate stress crack formation.
  • optical properties like transparency generally decrease with increasing density.
  • bimodal polyethylenes depend, firstly, on the properties of the components present. Secondly, the quality of mixing of the high molecular weight component and the low molecular weight component is of particular importance for the mechanical properties of the polyethylene. A poor mixing quality results, inter alia, in a low stress cracking resistance and adversely affects the creep behavior of pressure pipes made of polyethylene blends.
  • Such bimodal polyethylene blends are often produced using reactor cascades, i.e. two or more polymerization reactors are connected in series, and the polymerization of the low molecular weight component occurs in one reactor and that of the high molecular weight component occurs in the next (cf. for example, M. Ratzsch, W. Nei ⁇ l "Bimodale Polymertechnik für der Basis von PP und PE” in "Auf holeen von Polymeren mit neuartigenstoff", pp. 3-25, VDI-Verlag, D ⁇ sseldorf 1995).
  • a disadvantage of this process is that relatively large amounts of hydrogen have to be added to produce the low molecular weight component.
  • the polymers obtained in this way therefore have a low content of vinyl end groups, especially in the low molecular weight component.
  • it is technically complex to prevent comonomers added in one reactor or hydrogen added as regulator from getting into the next reactor.
  • catalyst compositions comprising two or more different olefin polymerization catalysts of the Ziegler type or the metaliocene type is known.
  • the copolymers of ethylene with higher ⁇ -olefins such as propene, 1-butene, 1-pentene, 1-hexene or 1-octene known as LLDPE (linear low density polyethylene) which are formed using classical Ziegler-Natta catalysts based on titanium are different from an LLDPE which is prepared using a metaliocene.
  • LLDPE linear low density polyethylene
  • SCBD short chain branching distribution
  • WO 99/46302 describes a catalyst composition based on (a) an iron-pyridinebisimine component and (b) a further catalyst such as a zirconocene or Ziegler catalyst and their use for the polymerization of ethylene and olefins.
  • the bubble is inflated uniformly and simultaneously in machine and transverse direction under intensive cooling immediately before it reaches the frost line. This usually improves mechanical properties of the film. On the other hand it is not possible in all extrusion lines to adjust the upper cooling lip and thus the bubble shape.
  • the known ethylene copolymer blends still leave something to be desired in terms of the combination of good mechanical properties, good processability and and high optical qualities. It is further desirable to have films which have similar properties independently from the mode of extrusion by either the "conventional” or the "long stalk” method.
  • a polyethylene which comprises ethylene homopolymers and/or copolymers of ethylene with 1-alkenes and has a molar mass distribution width M w /M n of from 5 to 30, a density of from 0.92 to 0.955 g/cm 3 , a weight average molar mass M w of from 50000 g/mol to 500 000 g/mol and has from 0.01 to 20 branches/1000 carbon atoms and a z-average molar mass Mz of less than 1 Mio. g/mol.
  • the polyethylene of the invention has a molar mass distribution width M w /M n in the range from 5 to 30, preferably from 6 to 20 and particularly preferably from 7 to 15.
  • the density of the polyethylene of the invention is in the range from 0.92 to 0.955 g/cm 3 , preferably from 0.93 to 0.95 g/cm 3 and particularly preferably in the range from 0.935 to 0.945 g/cm 3 .
  • the weight average molar mass M w of the polyethylene of the invention is in the range from 50000 g/mol to
  • 500 000 g/mol preferably from 100 000 g/mol to 300 000 g/mol and particularly preferably from
  • the molar " mass distribution of the polyethylene of the invention can be monomodal, bimodal or multimodal.
  • a monomodal molar mass distribution means that the molar mass distribution has a single maximum.
  • a bimodal molar mass distribution means, for the purposes of the present patent application, that the molar mass distribution has at least two points of inflection on one flank starting from a maximum.
  • the molar mass distribution is preferably monomodal or bimodal, in particular bimodal.
  • the polyethylene of the invention has from 0.01 to 20 branches/1000 carbon atoms, preferably from 1 to 10 branches/1000 carbon atoms and particularly preferably from 3 to 8 branches/1000 carbon atoms.
  • the branches/1000 carbon atoms are determined by means of 13 C-NMR, as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and refer to the total content of CH 3 groups/1000 carbon atoms.
  • the z-average molar mass M 2 of the polyethylene of the invention is in the range of less than 1 Mio. g/mol, preferably from 250 000 g/mol to 700 000 g/mol and particularly preferably from 300 000 g/mol to 500 000 g/mol.
  • the definition of z-average molar mass M z is e.g. published in High Polymers Vol. XX, Raff und Doak, Interscience Publishers, John Wiley & Sons, 1965, S. 443.
  • Der HLMI of the polyethylene of the invention is preferably in the range of from 5 to 100 g/10min, preferably in the range of from 7 bis 60 g/10min and particularly preferably of from 9 to 50 g/10min.
  • the expression "HLMI” refers as known to the "high load melt index” and is determined at 190°C under a load of 21.6 kg (190°C/21.6 kg) in accordance with ISO 1133.
  • the amount of the polyethylene of the invention with a molar mass of below 1 Mio. g/mol, as determined by GPC, in the standard determination of the molecular weight distribution, is preferably above 95.5 % by weight, preferably above 96 % by weight and particularly preferably above 97 % by weight. This is determined in the usual course of the molar mass distribution measurement by applying the WIN GPC software.
  • the polyethylene of the invention has preferably at least 0.5 vinyl groups/1000 carbon atoms, preferably from 0.6 to 3 vinyl groups/1000 carbon atoms and particularly preferably from 0.7 to 2 vinyl groups/1000 carbon atoms.
  • the content of vinyl groups/1000 carbon atoms is determined by means of IR, ASTM D 6248-98.
  • Vinyl groups are usually attributed to a polymer termination reaction after an ethylene insertion, while vinylidene end groups are usually formed after a polymer termination reaction after a comonomer insertion.
  • Vinylidene and vinyl groups can subsequently be functionalized or crosslinked, with vinyl groups usually being more suitable for these subsequent reactions. Preference is given to at least 0.5 vinyl groups/1000 carbon atoms, preferably from 0.5 to 10 vinyl groups/1000 carbon atoms and particularly preferably from 0.7 to 5 vinyl groups/1000 carbon atoms being present in the 20% by weight of the polyethylene having the lowest molar masses. This can be determined by sumble-nonsolvent fractionation, later called Holtrup fractionation as described in W. Holtrup, Makromol. Chem. 178, 2335 (1977) coupled with IR measurement of the different fractions, with the vinyl groups being measured in accordance with ASTM D 6248-98. Xylene and ethylene glycol diethyl ether at 130°C were used as solvents for the fractionation. 5 g of polyethylene were used and were divided into 8 fractions.
  • the polyethylene of the invention preferably has at least 0.05 vinylidene groups/1000 carbon atoms, in particular from 0.1 to 1 vinylidene groups/1000 carbon atoms and particularly preferably from 0.14 to 0.4 vinylidene groups/1000 carbon atoms.
  • the determination is carried out in accordance with ASTM D 6248-98.
  • the 5-50% by weight of the polyethylene of the invention having the lowest molar masses preferably 10-40% by weight and particularly preferably 15-30% by weight, have a degree of branching of less than 12 branches/1000 carbon atoms.
  • This degree of branching in the part of the polyethylene having the lowest molar masses is preferably from 0.01 to 10 branches/1000 carbon atoms and particularly preferably from 0.1 to 6 branches/1000 carbon atoms.
  • the 5-50% by weight of the polyethylene of the invention having the highest molar masses, preferably 10-40% by weight and particularly preferably 15-30% by weight have a degree of branching of more than 1 branch/1000 carbon atoms.
  • This degree of branching in the part of the polyethylene having the highest molar masses is preferably from 2 to 40 branches/1000 carbon atoms and particularly preferably from 5 to 20 branches/1000 carbon atoms.
  • the part of the polyethylene having the lowest or highest molar mass is determined by the method of solvent- nonsolvent fractionation, later called Holtrup fractionation as described in W. Holtrup, Makromol. Chem. 178, 2335 (1977) and coupled with IR or NMR analysis of the different fractions. Xylene and ethylene glycol diethyl ether at 130°C were used as solvents and nonsolvent for the fractionation. 5 g of polyethylene were used and were divided into 8 fractions. The fractions are • subsequently examined by 13 C-NMR spectroscopy.
  • the degree of branching in the various polymer fractions can be determined by means of 13 C-NMR as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989).
  • the degree of branching is the total CH 3 content/1000 carbon atoms in the low or high molecular weight fractions.
  • the polyethylene of the invention preferably has from 0.1 to 20 branches of side chains larger than CH 3 / 000 carbon atoms, prefereably side chains from C 2 -C 6 /1000 carbon atoms, preferably from 1 to 10 branches of side chains larger than CH 3 /1000 carbon atoms, prefereably side chains from C 2 -C 6 /1000 carbon atoms and particularly preferably from 2 to 6 branches of side chains larger than CH 3 /IOOO carbon atoms, prefereably side chains from C 2 -C 6 /1000 carbon atoms.
  • the amount of branches of side chains larger than CH 3 /1000 carbon atoms are determined by means of 13 C-NMR, as determined by James C. Randall, JMS-REV. Macromol. Chem.
  • the ratio of Eta-values of the polyethylene of the invention Eta(vis)/Eta(GPC) is preferably less than 0.95, preferably less than 0.93 and particularly preferably less than 0.90.
  • Eta(vis) is the intrinsic viscosity as determined according to ISO 1628-1 and -3 in Decalin at 135°C.
  • Eta(GPC) ist he viscosity as determined by GPC (gel permeation chromatographie) according to DIN 55672, wherein 1 ,2,4-Trichlorobenzene is used instead of THF and the determination is carried out at 140°C instead of room temperature.
  • the part of the polyethylene having a molar mass of less than 10 000 g/mol, preferably less than 20 000 preferably has a degree of branching of from 0 to 1.5 branches of side chains larger than CH 3 /1000 carbon atoms, prefereably side chains from C 2 - C ⁇ /IOOO carbon atoms.
  • the polyethylene of the invention with 1-butene, 1-hexene or 1-octene as the -olefin the part of the polyethylene having a molar mass of less than 10 000 g/mol, preferably less than 20 000, preferably has a degree of from 0 to 1.5 ethyl, butyl or hexyl branches of side chains/1000 carbon atoms.
  • the part of the polyethylene having a molar mass of less than 10 000 g/mol, preferably less than 20 000 having a degree of branching of from 0.1 to 0.9 ethyl, butyl or hexyl branches of side chains/1000 carbon atoms.
  • the polyethylene of the invention preferably has a mixing quality measured in accordance with ISO 13949 of less than 3, in particular from 0 to 2.5. This value is based on the polyethylene taken directly from the reactor, i.e. the polyethylene powder without prior melting in an extruder. This polyethylene powder is preferably obtainable by polymerization in a single reactor.
  • the polyethylene of the invention preferably has a degree of long chain branching ⁇ (lambda) of from 0 to 2 long chain branches/10 000 carbon atoms and particularly preferably from 0.1 to 1.5 long chain branches/10 000 carbon atoms.
  • the degree of long chain branching ⁇ (lambda) was measured by light scattering as described, for example, in ACS Series 521 , 1993, Chromatogra- phy of Polymers, Ed. Theodore Provder; Simon Pang and Alfred Rudin: Size-Exclusion
  • 1-alkenes which are the comonomers which can be present, either individually or in a mixture with one another, in addition to ethylene in the ethylene copolymer part of the polyethylene of the invention, it is possible to use all 1-alkenes having from 3 to 12 carbon atoms, e.g. propene, 1- butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.
  • the ethylene copolymer preferably comprises 1-alkenes having from 4 to 8 carbon atoms, e.g.
  • the polyethylene of the invention can further comprise of from 0 to 6 % by weight, prefereably 0,1 to 1 by weight of auxiliaries and/or additives known per se, e.g. processing stabilizers, stabilizers against the effects of light and heat, customary additives such as lubricants, antioxidants, antiblocking agents and antistatics, and also, if appropriate, dyes.
  • auxiliaries and/or additives known per se, e.g. processing stabilizers, stabilizers against the effects of light and heat, customary additives such as lubricants, antioxidants, antiblocking agents and antistatics, and also, if appropriate, dyes.
  • fiuoroelastomers are known as such as processing aids and are commercially available, for example, under the trade names Viton® and Dynamar® (cf. also, for example, US-A-3125547). They are preferably added in amounts of from 10 to 1000 ppm, particularly preferably from 20 to 200 ppm, based on the total mass of the polymer blend according to the invention.
  • a granulation apparatus e.g. a twin-screw kneader (ZSK), Farrel kneader or Kobe kneader.
  • the granulated mixture can also be processed directly on a film production plant.
  • Films in which the polyethylene of the invention is present as a significant component are ones which contain from 50 to 100% by weight, preferably from 60 to 90% by weight, of the polyethylene of the invention, based on the total polymer material used for manufacture. In particular, films in which one of the layers contains from 50 to 100% by weight of the polyethylene of the invention are also included.
  • the films are produced by plastification of the polyethylene of the invention at a melt temperature in the range of from 190 to 230 °C, forcing of the plastificised polyethylene through an annular die and cooling.
  • the film can further comprise of from 0 to 30 % by weight, prefereably 0.1 to 3 by weight of auxiliaries and/or additives known per se, e.g. processing stabilizers, stabilizers against the effects of light and heat, customary additives such as lubricants, antioxidants, antiblocking agents and antistatics, and also, if appropriate, dyes.
  • the polyethylenes of the invention can be used to prepare films with a thickness of from 5 ⁇ m to 2.5 mm.
  • the films can e.g. be prepared via blown film extrusion with a thickness of from 5 ⁇ m to 250 ⁇ m or via flat film extrusion, like cast film extrusion with a thickness of from 10 ⁇ m bis 2.5 mm.
  • blown film extrusion the polyethylene melt is forced through an annular die.
  • the bubble that is formed is inflated with air and hauled off at a higher speed than the die outlet speed.
  • the bubble is intensively cooled by a current of air so that the temperature at the frost line is lower than the crystallite melting point.
  • the bubble dimensions are fixed here.
  • the bubble is then collapsed, trimmed if necessary and rolled up using a suitable winding instrument.
  • the polyethylenes of the invention can be extruded by either the "conventional” or the "long stalk” method.
  • the flat films can be obtained e.g. in chill roll lines or thermoforming film lines.
  • composite films from the inventive polyethylene can be produced on coating and laminating lines.
  • composite films wherein paper, aluminium or fabric substrates are incorporated into the composite structure.
  • the films can be monolayered or multilayered, obtained by coextrusion and are preferably monolayered.
  • the polyethylenes of the invention are, for example, very suitable for producing films on blown film and cast film plants at high outputs.
  • the films display very good mechanical properties, high shock resistance and high ultimate tensile strength together with very good optical properties, in particular transparency and gloss. They are suitable, in particular, for the packing sector, for example as heat sealing films, both for heavy duty sacks and also for the food sector. Furthermore, the films display only a low blocking tendency and can therefore be handled by machines with only small additions, if any, of lubricants and antiblocking agents.
  • the films of the invention are particularly suitable as stretch films, hygienic films, films for office uses, sealing layers, composite and laminating films.
  • the films are especially suitable in applications requiring high clarity and gloss such as carrier bags to permit high quality printing, laminating films in foodstuff applications, since the films of the invention also have a very low odour and taste level and automatic packaging films, since the film can be processed on high- speed lines.
  • the films of the invention with a thickness of 50 ⁇ m have preferably a haze, as determined by ASTM D 1003-00 on a BYK Gardener Haze Guard Plus Device on at least 5 pieces of film 10x10 cm below 22 %, preferably of from 5 to 21 % and particularly preferably of from 7 to 20%.
  • the dart drop impact of the film with a thickness of 50 ⁇ m as determined by ASTM D 1709 Method A is preferably above 80 g, preferably of from 85 to 400 g and particularly preferably of from 90 to 350 g.
  • the clarity of the film with a thickness of 50 ⁇ m as determined by ASTM D 1746 - 03 on a BYK Gardener Haze Guard Plus Device, calibrated with calibration cell 77.5, on at least 5 pieces of film 10x10 cm is preferably at least 95 %, preferably of from 96 to 100 % and particularly preferably of from 97 to 99 %.
  • the gloss 45° of the film with a thickness of 50 ⁇ m as determined by ASTM D 2457 -03 on a gloss meter 45° with a vacuum plate for fixing the film, on at least 5 pieces of film is preferably at least 46, preferably of from 47 to 80 and " particularly preferably of from 49 to 70.
  • the scrap obtained during the production of these films can be recycled.
  • Film trimmings are compacted or ground and fed to a side extruder in which they are melted and returned to the main extruder.
  • the film residues should be reground to grains of a size that can be fed into the feed section of the processing machinery together with the virgin polyethylene.
  • the films obtained with regrind inventive films in one layer do not show any significant deterioration of the properties compared to films without regrind.
  • the polyethylene of the invention is obtainable using the catalyst system of the invention and in particular its preferred embodiments.
  • a catalyst system for preparing the polyethylenes of the invention and a process for preparing the polyethylene of the invention by polymerization of ethylene or copolymerization of ethylene with 1-alkenes with 3 to 12 carbon atoms in the presence of the catalyst system.
  • a preferred process for preparing the polyethylene of the invention by polymerization of ethylene or copolymerization of ethylene with one or several 1-alkenes of formula R 1 CH CH 2 , in der R 1 is hydrogen or an alkyl radical with 1 bis 10 carbon atoms in the presence of the catalyst system at a temperature of from 20 to 200 °C and a pressure of from 0,5 to 100 bar, equivalent to 0,05 to 1 MPa.
  • 1-alkenes are e.g. ethylene, propylene, 1-butene, 1- hexene, 4-methyl-1-pentene or 1-octene.
  • the process of the invention results in polyethylenes with a low transition metal and halogen content due to the high activity of the catalyst.
  • the polyethylenes therefore show high colour stability, corrosion resistance and clarity.
  • the present invention further provides a catalyst composition comprising at least two different polymerization catalysts of which A) is at least one polymerization catalyst based on a hafnocene
  • (A) and B) is at least one polymerization catalyst based on an iron component having a tridentate ligand bearing at least two aryl radicals with each bearing a halogen or tert. alkyl substituent in the ortho-position (B).
  • the invention further provides a process for the polymerization of olefins in the presence of the catalyst composition of the invention.
  • Hafnocene catalyst components are, for example, cyclopentadienyl complexes.
  • the cyclopenta- dienyl complexes can be, for example, bridged or unbridged biscyclopentadienyl complexes as described, for example, in EP 129 368, EP 561 479, EP 545 304 and EP 576 970, monocyclo- pentadienyl complexes such as bridged amidocyclopentadienyl complexes described, for example, in EP 416 815, multinuclear cyclopentadienyl complexes as described in EP 632 063, pi-ligand-substituted tetrahydropentalenes as described in EP 659 758 or pi-ligand-substituted tetrahydroindenes as described in EP 661 300.
  • hafnocenes (A) are hafnium complexes of the general formula (I)
  • X B is fluorine, chlorine, bromine, iodine, hydrogen, C ⁇ -C ⁇ 0 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, -OR 6B or -NR 6B R 7B , or two radicals X B form a substituted or unsubstituted diene ligand, in particular a 1 ,3-diene ligand, and the radicals X B are identical or different and may be joined to one another,
  • E -E are each carbon or not more than one E to E is phosphorus or nitrogen, preferably carbon, is 1 , 2 or 3 and is, depending on the valence of Hf, such that the metaliocene complex of the general formula (VI) is uncharged,
  • R 6B and R 7B are each C ⁇ -C ⁇ 0 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part and
  • R 1B to R 5B are each, independently of one another hydrogen, C ⁇ C 22 -alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn bear C-i-Cjo-alkyl groups as substituents, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 16 carbon SB atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, NR 2 , N(SiR 8B 3 ) 2 , OR 8B , OSiR 8B 3 , SiR 8B 3 , where the organic radicals R 1B -R 5B may also be substituted by halogens and/or two radicals R 1B -.R 5B , in particular vicinal radicals, may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 1D -R 5
  • radicals R 8B can be identical or different and can each be d-C ⁇ -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, C ⁇ -C 4 -alkoxy or C 6 -C 10 -aryloxy and
  • R 9B to R 13B are each, independently of one another, hydrogen, C,--C 22 -alkyl, 5- to 7- membered cycloalkyl or cycloalkenyl which may in turn bear C ⁇ -C 1( ,-alkyl groups as substituents, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl part and 6-21 carbon atoms in the aryl part, NR 1 B 2 , N(SiR 1 B 3 ) 2 , OR 14B , OSiR 14B 3 , SiR 1 B 3 , where the organic radicals R 9B -R 13B may also be substituted by halogens and/or two radicals R 9B -R 13B , in particular vicinal radicals, may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 9B
  • radicals R B are identical or different and are each C ⁇ C ⁇ -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 - aryl, or C 6 -C 10 -aryloxy,
  • E ⁇ B -E 10B are each carbon or not more than one E 6B to E 10B is phosphorus or nitrogen, preferably carbon,
  • R -R are identical or different and are each a hydrogen atom, a halogen atom, a trimethylsilyl group, a C,-C 10 -alkyl group, a C,-C ⁇ o-fluoroalkyl group, a C 6 -C 10 - fluoroaryl group, a C 6 -C 10 -aryl group, a d-do-alkoxy group, a C 7 -C 15 - alkylaryloxy group, a C 2 -C 10 -alkenyl group, a C-r-do-arylalkyl group, a C 8 -C 40 - arylalkenyl group or a C 7 -C 40 -alkylaryl group or two adjacent radicals together with the atoms connecting them form a saturated or unsaturated ring having from 4 to 15 carbon atoms, and
  • M 2B -M 4B are each silicon, germanium or tin, or preferably silicon,
  • radicals R 22B are each, independently of one another, C ⁇ -C ⁇ 0 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 - cycloalkyl, C 7 -C 18 -alkylaryl or Si(R 23B ) 3 ,
  • R 23B is hydrogen, C ⁇ -C 15 -aryl which may in turn bear C 1 —C — alkyl groups as substituents or C 3 -C ⁇ 0 -cycloalkyl,
  • v is 1 or. when A 1B is an unsubstituted, substituted or fused, heterocyclic ring system may also be 0
  • a 1B can, for example together with the bridge R 158 , form an amine, ether, thioether or phosphine.
  • a 1B can also be an unsubstituted, substituted or fused, heterocyclic aromatic ring system which can contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen and phosphorus in addition to ring carbons.
  • Examples of 5-membered heteroaryl groups which can contain from one to four nitrogen atoms and/or a sulfur or oxygen atom as ring members in addition to carbon atoms are 2-furyl, 2-thienyl, 2-pyrrolyl, 3-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxa- diazol-5-yl, 1 ,3,4-oxadiazol-2-yl and 1 ,2,4-triazol-3-yl.
  • 6-membered heteroaryl groups which may contain from one to four nitrogen atoms and/or a phosphorus atom are 2-pyridinyl, 2- phosphabenzenyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl, 1 ,2,4-triazin-5-yl and 1 ,2,4-triazin-6-yl.
  • the 5-membered and 6-membered heteroaryl groups may also be substituted by d-Cm-alkyl, C 6 -C 10 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogens such as fluorine, chlorine or bromine or be fused with one or more aromatics or heteroaromatics.
  • benzo-fused 5-membered heteroaryl groups are 2-indolyI, 7-indolyl, 2-coumaronyl, 7- coumaronyl, 2-thionaphthenyl, 7-thionaphthenyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl and 7- benzimidazolyl.
  • benzo-fused 6-membered heteroaryl groups are 2-quinolyl, 8-quino- lyl, 3-cinnolyl, 8-cinnolyl, 1-phthalazyl, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalyl, 4- acridyl, 1-phenanthridyl and 1-phenazyl.
  • Naming and numbering of the heterocycles has been taken from L.Fieser and M. Fieser, Lehrbuch der organischen Chemie, 3 rd revised edition, Verlag Chemie, Weinheim 1957.
  • radicals X B in the general formula (I) are preferably identical, preferably fluorine, chlorine, bromine, C-,-C 7 -alkyl or aralkyl, in particular chlorine, methyl or benzyl.
  • the hafnocenes can be used in the Rac or pseudo-Rac form.
  • pseudo-Rac refers to complexes in which the two cyclopentadienyl ligands are in the Rac arrangement relative to one another when all other substituents of the complex are disregarded.
  • hafnocenes (A) are, inter alia, methylenebis(cyclope ⁇ tadienyl)hafnium dichloride, methylenebis(3-methylcyclopentadienyl)- hafnium dichloride, methylenebis(3-n-butylcyclopentadienyl)hafnium dichloride, methylene- bis(indenyl)hafnium dichloride, methylenebis(tetrahydroindenyl) hafnium dichloride, isopro- pylidenebis(cyclopentadienyl)hafnium dichloride, isopropylidenebis(3-trimethylsilylcyclopenta- dienyl)hafnium dichloride, isopropylidenebis(3-methylcyclopentadienyl)hafnium dichloride, iso- propylidenebis(3-n-butylcyclopentadieny
  • X B is fluorine, chlorine, bromine, d-C 4 -alkyl or benzyl, or two radicals X B form a substituted or unsubstituted butadiene ligand,
  • t is 1 or 2, preferably 2,
  • R 1B to R 5B are each hydrogen, Ci-C ⁇ -alkyl, C ⁇ -C ⁇ -aryl, NR 8B 2 , OSiR 8B 3 or Si(R 8B ) 3 and
  • R 9B to R 13B are each hydrogen, C r C 8 -alkyl or C ⁇ -C ⁇ -aryl, NR 14B 2 , OSiR 14B 3 or Si(R 14B ) 3
  • hafnocenes of the formula (II) in which the cyclopentadienyl radicals are identical are particularly useful.
  • Examples of particularly suitable compounds (A) of the formula (II) are, inter alia: bis(cyclopentadienyl)hafnium dichloride, bis(indenyl)hafnium dichloride, bis(fluorenyl)hafnium dichloride, bis(tetrahydroindenyl)hafnium dichloride, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(trimethylsilylcyclopentadienyl)hafnium dichloride, bis(trimethoxysilylcyclopenta- dienyl)hafnium dichloride, bis(ethylcyclopentadienyl)hafnium dichloride, bisfisobutylcyclopenta- dienyl)hafnium dichloride, bis(3-butenylcyclopentadienyl)hafnium dichloride, bis(methylcyclo- pentadienyl)haf
  • Suitable catalysts B) are transition metal complexes with at least one ligand of the general formulae (
  • -1C is nitrogen or phosphorus, in particular nitrogen
  • E 2C -E 4C are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon,
  • R-.3C are each, independently of one another, hydrogen C C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR 18C 2 , OR 18C , SIR 19C 3 , where the organic radicals R 1C -R 3C may also be substituted by halogens and/or two vicinal radicals R 1C -R 3C may also be joined to form a five-, six- or seven-membered ring, and/or. two vicinal radicals R 1C -R 3C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S,
  • R 4C -R 7C are each, independently of one another, hydrogen, C C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 18C 2l SiR 19C 3 , where the organic radicals R 4C -R 7C may also be substituted by halogens and/or two geminal or vicinal radicals R 4C -R 7C may also be joined to form a five-, six- or seven-membered ring, and/or two geminal or vicinal radicals R 4C -R 9C are .
  • R 6C is a bond to L 1C and/or R is a bond to L so that L forms a double bond to the carbon atom bearing R' and/or L 2C forms a double bond to the carbon atom bearing R 5C ,
  • u is 0 when E 2C -E 4C is nitrogen or phosphorus and is 1 when E 2C -E 4C is carbon, L 1C -L 2C are each, independently of one another, nitrogen or phosphorus, in particular nitrogen,
  • R 8C -R 11C are each, independently of one another, hydrogen, d-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in • the aryl part, halogen, NR 8C 2 , OR 18C , SiR 19C 3 , where the organic radicals R 8C -R 11C may also be substituted by halogens and/or two vicinal radicals R 8C -R 17C may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 8C -R 17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, and with the proviso that at least R 8C and R 10C are halogen or a
  • R 2C -R 17C are each, independently of one another, hydrogen, C C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR 1 ⁇ c 2 , OR 18C , SiR 19C 3 , where the organic radicals R 12C -R 17C may also be substituted by halogens and/or two vicinal radicals R 8C -R 17C may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 8C -R 17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S,
  • the indices v are each, independently of one another, 0 or 1 ,
  • the radicals X c are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, d-d 0 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 18C 2 , OR 18C , SR 18C , S0 3 R 18C , OC(0)R 18C , CN, SCN, ⁇ -diketonate, CO, BF 4 " , PF 6 " or a bulky noncoordinating anion and the radicals X c may be joined to one another,
  • the radicals R 180 are each, independently of one another, hydrogen, C ⁇ -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR 19C 3 , where the organic radicals R 8C may also be substituted by halogens or nitrogen- and oxygen-containing groups and two radicals R 18C may also be joined to form a five- or six-membered ring,
  • the radicals R 19C are each, independently of one another, hydrogen, C ⁇ -C 2 o-alkyl, C C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R 19C may also be substituted by halogens or nitrogen- and oxygen-containing groups and two radicals R 19C may also be joined to form a five- or six-membered ring, s is 1 , 2, 3 or 4, in particular 2 or 3,
  • D is an uncharged donor and t is from 0 to 4, in particular 0, 1 or 2.
  • E 2C to E 4C in a molecule can be identical or different. If E 1C is phosphorus, then E 2C to E C are preferably each carbon. If E 1C is nitrogen, then E 2C to E 4C are each preferably nitrogen or carbon, in particular carbon.
  • the substituents R 1C -R 3C and R 8C -R 17C can be varied within a wide range. Possible carboorganic substituents R 1C -R 3C and R 8C -R 17C are, for example, the following: C C 22 -alkyl which may be linear or branched, e.g.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 22 - alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or -terminal, e.g.
  • s0 be SU S tjt u ted by halogens such as fluorine, chlorine or bromine.
  • R 1C -R 3C and R 8C -R 17C can also be amino NR 18C 2 or N(SiR 19C 3 ) 2 , alkoxy or aryloxy OR 18C , for example dimethylamino, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy or halogen such as fluorine, chlorine or bromine.
  • Possible radicals R 19C in organosilicon substituents SiR 19C 3 are the same carboorganic radicals as have been described above for R 1C -R 3C , where two R 19C may also be joined to form a 5- or 6-membered ring, e.g.
  • SiR 19C 3 radicals may also be bound to E 2C -E C via an oxygen or nitrogen, for example trimethylsilyloxy, triethyl- silyloxy, butyldimethylsilyloxy, tributylsilyloxy or tri-tert-butylsilyloxy.
  • Preferred radicals R 1C -R 3C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl- or -dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.
  • Particularly preferred organosilicon substituents are trialkylsilyl groups having from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl groups.
  • Preferred radicals R 12C -R 17C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen.
  • R i3C and R 16C are each methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine or bromine and R 1 C , R 14C , R 15C and R 17C are each hydrogen.
  • Preferred radicals R 9C and R 11C are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine.
  • R 8C and R 10C are preferably a halogen such as fluorine, chlorine or bromine, particularly chlorine and R 9C and R 11C are each a d-C 22 -alkyl which may also be substituted by halogens, in particular a d-C 22 -n-alkyl which may also be' substituted by halogens, e.g. methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or a halogen such as fluorine, chlorine or bromine.
  • halogen such as fluorine, chlorine or bromine
  • R 8C and R 10C are a tertiary C r C 22 -alkyl radical, particularly tert. butyl and R 9C and R 11C are each hydrogen or a halogen such as fluorine, chlorine or bromine.
  • R 12C , R 4C , R 15C and R 17C are identical, R 13C and R 16C are identical, R 9C and R 11C are identical and R 8C and R 10C are identical. This is also preferred in the preferred embodiments described above.
  • the substituents R 4C -R 7C can be varied within a wide range.
  • Possible carboorganic substituents R 4C -R 7C are, for example, the following: C C 22 -alkyl which may be linear or branched, e.g.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 22 -alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
  • R C to R 7C may also be joined to form a 5-, 6- or 7-membered ring and/or two geminal radicals
  • R 4C -R 7C may be joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S and/or the organic radicals R 4C -R 7C may also be substituted by halogens such as fluorine, chlorine or bromine.
  • R 4C -R 7C may be amino NR 18C 2 or N(SiR 19C 3 )2.
  • R 19C in organosilicone substituents SiR 19C 3 are the same carboorganic radicals as have been described above for R 1C -R 3C , where two R 19C may also be joined to form a 5- or 6- membered ring, e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.
  • These SiR 19C 3 radicals can also be bound via nitrogen to the carbon bearing them.
  • R 8C is a bond to L 1C and/or R 7C is a bond to L 2C , so that L 1C forms a double bond to the carbon atom bearing R 4C and/or L 2C forms a double bond to the carbon atom bearing R 5C .
  • Preferred radicals R C -R 7C are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, ortho-dialkyl- or dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.
  • amide substituents NR 18C 2 in particular secondary amides such as dimethylamide, N-ethylmethylamide, diethylamide, N-methylprbpylamide, N-methylisopropylamide, N-ethyliso- propylamide, dipropylamide, diisopropylamide, N-methylbutylamide, N-ethylbutylamide, N-methyl- tert-butylamide, N-tert-butylisopropylamide, dibutylamide, di-sec-butylamide, diisobutylamide, tert- amyl-tert-butylamide, dipentylamide, N-methylhexylamide, dihexylamide, tert-amyl-tert- octylamide, dioctylamide, bis(2-ethylhexyl)amide, didecylamide, N-methyloc
  • L 1C and L 2C are each, independently of one another, nitrogen or phosphorus, in particular nitrogen, and when v is 0 can form a double bond with the carbon atom bearing R 4C or R 5C .
  • v is 1
  • L 1C and/or L 2C together with the carbon atom bearing R 4C or R 5C forms, in particular, an amido group -GR C R ⁇ c -N - or -CR 5C R 7C -NX
  • the ligands X c result, for example, from the choice of the appropriate starting metal compounds used for the synthesis of the iron complexes, but can also be varied afterward.
  • Possible ligands X c are, in particular, the halogens such as fluorine, chlorine, bromine or iodine, in particular chlorine.
  • Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl are also usable ligands X c .
  • ligands X c mention may be made, purely by way of example and in no way exhaustively, of trifluoroacetate, BF 4 " , PF 6 " and weakly coordinating or noncoordinating anions (cf., for example, S. Strauss in Chem. Rev. 1993, 93, 927-942), e.g. B(C 6 F 5 ) 4 ⁇ . Amides, alkoxides, sulfonates, carboxylates and ⁇ -diketonates are also particularly useful ligands X c . Some of these substituted ligands X are particularly preferably used since they are obtainable, from cheap and readily available starting materials.
  • a particularly preferred embodiment is that in which X c is dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluenesulfonate, acetate or acetylacetonate.
  • Variation of the radicals R 18C enables, for example, physical properties such as solubility to be 18C finely adjusted.
  • Possible carboorganic substituents R are, for example, the following: C C 20 - " alkyl which may be linear or branched, e.g.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 20 -alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
  • radicals R 18C may also be joined to form a 5- or 6-membered ring and the organic radicals R 8C may also be substituted by halogens such as fluorine, chlorine or bromine.
  • Possible radicals R 19C in organosilicon substituents SiR 9C 3 are the same radicals which have been described above for R 18C , where two radicals R 19C may also be joined to form a 5- or 6-membered ring, e.g.
  • d-C 1(r alkyl) such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and also vinyl allyl, benzyl and phenyl as radicals R 18C .
  • the number s of the ligands X c depends on the oxidation state of the iron. The number s can thus not be given in general terms.
  • the oxidation state of the iron in catalytically active complexes is usually known to those skilled in the art. However, it is also possible to use complexes whose oxidation state does not correspond to that of the active catalyst. Such complexes can then be appropriately reduced or oxidized by means of suitable activators. Preference is given to using iron complexes in the oxidation state +3 or +2.
  • the number t of the ligands D can be from 0 to 4 and is often dependent on the solvent in which the iron complex is prepared and the time for which the resulting complexes are dried and can therefore also be a nonintegral number such as 0.5 or 1.5. In particular, t is 0, 1 to 2.
  • the complexes (B) are of formula (IV) where
  • E 2C -E 4C are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon,
  • R -R are each, independently of one another, hydrogen, d-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR 18C 2 , OR 18C , SiR 19C 3 , where the organic radicals R 1C -R 3C may also be substituted by halogens and/or two vicinal radicals R 1C -R 3C may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 1C -R 3C are bound to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S,
  • R 4C -R 5C are each, independently of one another, hydrogen, C ⁇ -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 18C 2 , SiR 19C 3 , where the organic radicals R 4C -R 5C may also be substituted by halogens,
  • 2C r-4C u is 0 when E -E is nitrogen or phosphorus and is 1 when E -E is carbon
  • L -L are each), independently of one another, nitrogen or phosphorus, in particular nitrogen,
  • R' 8C R 11C are each, independently of one another, d-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR 18C 2 , OR 18C , SiR 19C 3 , where the organic radicals R 8C -R 11C may also be substituted by halogens and/or two vicinal radicals R 8C -R 17C may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 8C -R 17C are joined to form a five-, six- or seven-membered heterocycle containing at least one atom from the group consisting of N, P, O and S, and with the proviso that at least R 8C and R 10C are halogen or a tert. d
  • R 12C _ R 17C are each> i nc j e p en dently of one another, hydrogen, d-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 - aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, halogen, NR 18C 2 , OR 18C , SiR 9C 3 , where the organic radicals R 12C -R 17C may also be substituted by halogens and/or two vicinal radicals R 8C -R 17C may also be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R 8C -R 17C are joined to form a five-, six- or seven-membered heterocycle containing at least one-atom from the group consisting of N, P, O or S,
  • the indices v are each, independently of one another, 0 or 1 ,
  • the radicals X c are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, d-C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 18C 2 , OR 18C , SR 18C , S0 3 R 18C , ⁇ OC(0)R 18C , CN, SCN, ⁇ -diketonate, CO, BF 4 ⁇ , PF 6 " or a bulky noncoordinating anion and the radicals X c may be joined to one another,
  • the radicals R 18C are each, independently of one another, hydrogen, C ⁇ -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 2D -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR 19C 3 , where the organic radicals R 18G may also be substituted by halogens and nitrogen- and oxygen-containing groups and two radicals R 18C may also be joined to form a five- or six-membered ring,
  • the radicals R 19C are each, independently of one another, hydrogen, C ⁇ -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, where the organic radicals R 19C may also be substituted by halogens or nitrogen- and oxygen-containing groups and two radicals R 19C may also be joined to form a five- or six-membered ring,
  • s is 1 , 2, 3 or 4, in particular 2 or 3,
  • D is an uncharged donor
  • t is from 0 to 4, in particular 0, 1 or 2.
  • R C -R 5C can be varied within a wide range.
  • Possible carboorganic substituents R 4C -R 5C are, for example, the following: hydrogen, C-
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 22 -alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
  • halogens such as fluorine, chlorine or bromine.
  • R 4C -R 5C can be amino NR 18C 2 or N(SiR 19C 3 ) 2 , for example dimethylamino, N-pyrrolidinyl or picolinyl.
  • Possible radicals R 19C in organosilicon substituents SiR 9C 3 are the same carboorganic radicals as described above for R 1C -R 3C , where two radicals R 19G may also be joined to form a 5- or 6-membered ring, e.g.
  • SiR 19C 3 radicals can also be bound via nitrogen to the carbon bearing them.
  • Preferred radicals R C -R 5C are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl, in particular methyl.
  • the substituents R 8C -R 17G can be varied within a wide range.
  • Possible carboorganic substituents R 8C -R 17C are, for example, the following: C C 22 -alkyl which may be linear or branched, e.g.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 22 -alkenyl which may be linear, cyclic or branched and in which the double may be internal or terminal, e.g.
  • halogens such as fluorine, chlorine or bromine.
  • R 8C -R 17G I ⁇ * ⁇ .of can be halogen such as fluorine, chlorine, bromine, ammo NR 2 or N(SiR 3 ) 2 , alkoxy or aryloxy OR 180 , for example dimethylamino, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy.
  • Possible radicals R 19G in organosilicon substituents SiR 19C 3 are the same carboorganic radicals which have been mentioned above for R 1C -R 3C , where two radicals R 19G may also be joined to form a 5- or 6-membered ring, e.g.
  • SiR 19G 3 radicals can also be bound via an oxygen or nitrogen, for example trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or tritert-butylsilyloxy.
  • Preferred radicals R 12G -R 17G are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, h-heptyi, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen.
  • R 3G and R 16G are each methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, nn--ooccttyyll,, vviinnyyll,, aallllyl, benzyl, phenyl, fluorine, chlorine or bromine and R 12C , R 14G , R 15C and R 17G are each hydrogen.
  • Preferred radicals R 9C and R 11G are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyi, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine.
  • R 8G and R 10C are preferably a halogen such as fluorine, chlorine or bromine, particularly chlorine and R 9C and R 11G are each a d-C 22 -alkyl which may also be substituted by halogens, in particular a C 1 -C 22 -n-alkyl which may also be substituted by halogens, e.g. methyl, trifluoromethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or a halogen such as fluorine, chlorine or bromine.
  • halogen such as fluorine, chlorine or bromine
  • R 8C and R 10C are a tertiary C C 22 -alkyl radical, particularly tert. butyl and R 9C and R 11C are each hydrogen or a halogen such as fluorine, chlorine or bromine.
  • R 12C , R 14G , R 15G and R 17G are identical, R 13C and R 16G are identical, R 9G and R 11C are identical and R 8G and R 10C are identical. This is also preferred in the preferred embodiments described above.
  • Preferred complexes B) are 2,6-Bis[1-(2-tert.butylphenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1-(2- tert.butyl-6-chlorophenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1 -(2-chloro-6-methyl- phenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1-(2,4-dichlorophenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1 -(2,6-dichlorophenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1- (2,4-d ⁇ chlorophenylimino) ⁇ t ⁇ ethyl]pyridine iron(ll) dichloride, 2,6-Bis[1 -(
  • transition metal complex (A) or catalyst (A) means a hafnocene (A).
  • the molar ratio of transition metal complex A) to polymerization catalyst B) is usually in the range from 1 :100 to 100:1 , preferably from 1 :10 to 10:1 and particularly preferably from 1 :1 to 5:1.
  • a transition metal complex A) is used as sole catalyst under the same reaction conditions in the homopolymerization or copolymerization of ethylene, it preferably produces a higher Mw than does the complex (B) when it is used as sole complex under the same reaction conditions.
  • the preferred embodiments of the complexes (A) and (B) are likewise preferred in combinations of the two complexes.
  • transition metal complex A When a transition metal complex A) is used as sole catalyst under the same reaction conditions in the homopolymerization or copolymerization of ethylene, it preferably produces a higher Mw than does the complex (B) when it Is used as sole complex under the same reaction conditions.
  • the catalyst composition of the invention can be used alone or together with further components as catalyst system for olefin polymerization. Furthermore, we have found catalyst systems for olefin polymerization comprising
  • the hafnocene (A) and/or the iron complex (B) sometimes have only a low polymerization activity and are then brought into contact with one or more activators, viz. the component (C), in order to be able to display a good polymerization activity.
  • the catalyst system therefore optionally further comprises, as component (C) one or more activating compounds, preferably one or two activating compounds (C).
  • the catalyst system of the invention preferably comprises one or more activators (C)..
  • one or more activating compounds (C) are advantageous.
  • the activation of the transition metal complex (A) and of the iron complex (B) of the catalyst composition can be carried out using the same activator or activator mixture or different activators.
  • the activator or activators (C) can in each case be used in any amounts based on the complexes (A) and (B) of the catalyst composition of the invention. They are preferably used in an excess or in stoichiometric amounts, in each case based on the complex (A) or (B) which they activate.
  • the amount of activating compound(s) to be used depends on the type of the activator (C).
  • the molar ratio of transition metal complex (A) to activating compound (C) can be from 1 :0.1 to 1 :10000, preferably from 1 :1 to 1 :2000.
  • the molar ratio of iron complex (B) to activating compound (C) is also usually in the range from 1 :0.1 to 1 :10000, preferably from 1 :1 to 1 :2000.
  • Suitable compounds (C) which are able to react with the transition metal complex (A) or the iron complex (B) to convert it into a catalytically active or more active compound are, for example, compounds such as an aluminoxane, a strong uncharged Lewis acid, an ionic compound having a Lewis-acid cation or an ionic compound containing a Br ⁇ nsted acid as cation.
  • aluminoxanes it is possible to use, for example, the compounds described in WO 00/31090.
  • Particularly useful aluminoxanes are open-chain or cyclic aluminoxane compounds of the general formula (X) or (XI)
  • R 1D -R 4D are each, independently of one another, a C ⁇ -C 6 -alkyl group, preferably a methyl, ethyl, butyl or isobutyl group and I is an integer from 1 to 40, preferably from 4 to 25.
  • a particularly useful aluminoxane compound is methylaluminoxane.
  • oligomeric aluminoxane compounds are usually prepared by controlled reaction of a solution of a trialkylaluminum, in particular trimethylaluminum, with water.
  • the oligomeric aluminoxane compounds obtained are in the form of mixtures of both linear and cyclic chain molecules of various lengths, so that I is to be regarded as a mean.
  • the aluminoxane compounds can also be present in admixture with other metal alkyls, usually aluminum alkyls.
  • Aluminoxane preparations suitable as component (C) are commercially available.
  • modified aluminoxanes in which some of the hydrocarbon radicals have been replaced by hydrogen atoms or.alkoxy, aryloxy, siloxy or amide radicals can also be used in place of the aluminoxane compounds of the formula (X) or (XI) as component (C).
  • the transition metal complex A) or the iron complex B) and the aluminoxane compounds in such amounts that the atomic ratio of aluminum from the aluminoxane compounds including any aluminum alkyl still present to the transition metal from the transition metal complex (A) is in the range from 1 :1 to 2000:1 , preferably from 10:1 to 500:1 and in particular in the range from 20:1 to 400:1.
  • the atomic ratio of aluminum from the aluminoxane compounds including any aluminum alkyl still present to the iron from the iron complex (B) is usually in the range from 1 :1 to 2000:1 , preferably from 10:1 to 500:1 and in particular in the range from 20:1 to 400:1.
  • a further class of suitable activating components (C) are hydroxyaluminoxanes. These can be prepared, for example, by addition of from 0.5 to 1.2 equivalents of water, preferably from 0.8 to 1.2 equivalents of water, per equivalent of aluminum to an alkylaluminum compound, in particular triisobutylaluminum, at low temperatures, usually below 0°C. Such compounds and their use in olefin polymerization are described, for example, in WO 00/24787.
  • the atomic ratio of aluminum from the hydroxyaluminoxane compound to the transition metal from the transition metal complex (A) or the iron complex (B) is usually in the range from 1 :1 to 100:1 , preferably from 10:1 to 50:1 and in particular in the range from 20:1 to 40:1. Preference is given to using a hafnocene dialkyl compound (A).
  • M 2D is an element of group 13 of the Periodic Table of the Elements, in particular B, Al or Ga, preferably B,
  • X 1D , X 2D and X 3D are each hydrogen, d-do-alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part or fluorine, chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl.
  • Lewis acids are given in WO 00/31090.
  • Compounds which are particularly useful as component (C) are boranes and boroxins such as trialkylborane, triarylborane or trimethylboroxin. Particular preference is given to using boranes which bear at least two perfluorinated aryl radicals.
  • XII compounds of the general formula (XII) in which X 1D , X 2D and X 3D are identical, for example triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethylphenyl)borane, tris(3,5- difluorophenyl)borane or tris(3,4,5-trifluorophenyl)borane.
  • triphenylborane tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane
  • Suitable compounds (C) are preferably prepared by reaction of aluminum or boron compounds of the formula (XII) with water, alcohols, phenol derivatives, thiophenol derivatives or aniline derivatives, with halogenated and especially perfluorinated alcohols and phenols being of particular importance.
  • particularly useful compounds are pentafluorophenol, 1 ,1-bis(pentafluoro- phenyl)methanol and 4-hydroxy-2,2',3,3',4',5,5',6,6'-nonafluorobiphenyl.
  • Examples of combina- tions of compounds of the formula (XII) with Broenstedt acids are, in particular, trimethylalumi- num/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl)methanol, trimethylalumi- num/4-hydroxy-2,2',3,3',4',5,5',6,6'-nonafluorobiphenyl, triethylaluminum/pentafluorophenol and triisobutylaluminum/pentafluorophenol and triethylaluminum/4,4'-dihydroxy-2,2',3,3',5,5',6,6'- octafluorobiphenyl hydrate.
  • R 1D is an OH group, such as, for example, in boronic acids and borinic acids.
  • bori ⁇ ic acids having perfluorinated aryl radicals for example (C 6 F 5 ) 2 BOH.
  • Strong uncharged Lewis acids suitable as activating compounds (C) also include the reaction products of the reaction of a boronic acid with two equivalents of an aluminum trialkyl or the reaction products of the reaction of an aluminum trialkyl with two equivalents of an acidic fluorinated, in particular perfluorinated, carbon compound such as pentafluorophenol or bis(pentafluorophenyl)borinic acid.
  • Suitable ionic compounds having Lewis-acid cations include salt-like compounds of the cation of the general formula (XIII)
  • M is an element of groups 1 to 16 of the Periodic Table of the Elements
  • Q t to Q z are simply negatively charged radicals such as C ⁇ -C 2a -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl part and from 1 to 28 carbon atoms in the alkyl part, C 3 -C 10 -cycloalkyl which may bear d-C 10 -alkyl groups as substituents, halogen, d-C 28 -alkoxy, C 6 -C 15 - aryloxy, silyl or mercaptyl groups,
  • a is an integer from 1 to 6 and
  • z is an integer from 0 to 5
  • d corresponds to the difference a-z, but d is greater than or equal to 1.
  • Particularly useful cations are carbonium cations, oxonium cations and sulfonium cations and also cationic transition metal complexes. Particular mention may be made of the triphenylmethyl cation, the silver cation and the 1 ,1 -dimethylferrocenyl cation. They preferably have noncoordina- ting counterions, in particular boron compounds as are also mentioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.
  • Salts having noncoordinating anions can also be prepared by combining a boron or aluminum compound, e.g. an aluminum alkyl, with a second compound which can react to link two or more boron or aluminum atoms, e.g. water, and a third compound which forms with the boron or aluminium compound an ionizing ionic compound, e.g. triphenylchloromethane, or optionally a base, preferably an organic nitrogen-containing base, for example an amine, an aniline derivative or a nitrogen heterocycle.
  • a fourth compound which likewise reacts with the boron or aluminum compound e.g. pentafluorophenol, can be added.
  • Ionic compounds containing Br ⁇ nsted acids as cations preferably likewise have noncoordinating counterions.
  • Br ⁇ nsted acid particular preference is given to protonated amine or aniline derivatives.
  • Preferred cations are N,N-dimethylani!inium, N,N-dimethylcyc!ohexylammonium and N,N-dimethylbenzylammonium and also derivatives of the latter two.
  • component (C) Compounds containing anionic boron heterocycles as are described in WO 9736937 are also suitable as component (C), in particular dimethylanilinium boratabenzenes or trityl boratabenzenes.
  • Preferred ionic compounds C) contain borates which bear at least two perfluorinated aryl radicals. Particular preference is given to N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and in particular N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate or trityl tetrakispentafluoro- phenylborate.
  • borate anions it is also possible for two or more borate anions to be joined to one another, as in the dianion [(C 6 F 5 ) 2 B-C 6 F 4 -B(C 6 F 5 ) 2 j 2" , or the borate anion can be bound via a bridge to a suitable functional group on the support surface.
  • the amount of strong, uncharged Lewis acids, ionic compounds having Lewis-acid cations or ionic compounds containing Br ⁇ nsted acids as cations is preferably from 0.1 to 20 equivalents, more preferably from 1 to 10 equivalents and particularly preferably from 1 to 2 equivalents, based on the transition metal complex (A) or the iron complex (B).
  • Suitable activating compounds (C) also include boron-aluminum compounds such as di[bis(penta- fluorophenylboroxy)]methylalane. Examples of such boron-aluminum compounds are those disklosed in WO 99/06414.
  • Preferred mixtures comprise aluminoxanes, in particular methylaluminoxane, and an ionic compound, in particular one containing the tetrakis(pentafluorophenyl)borate anion, and/or a strong uncharged Lewis acid, in particular tris(pentafluorophenyl)borane or a boroxin.
  • Both the transition metal complex (A) or the iron complex (B) and the activating compounds (C) are preferably used in a solvent, preferably an aromatic hydrocarbon having from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or a mixture thereof.
  • a solvent preferably an aromatic hydrocarbon having from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or a mixture thereof.
  • a further possibility is to use an activating compound (C) which can simultaneously be employed . as support (D).
  • Such systems are obtained, for example, from an inorganic oxide treated with zirconium alkoxide and subsequent chlorination, e.g. by means of carbon tetrachloride. The preparation of such systems is described, for example, in WO 01/41920.
  • aluminoxane as activator (C) for the iron complex (B) are particularly useful joint activators (C) are the reaction products of aluminum compounds of the formula (XII) with perfluorinated alcohols and phenols.
  • transition metal complex (A) and the iron complex (B) it is often advantageous to use the complexes in the form of a solid, i.e. for them to be applied to a solid support (D). Furthermore, the supported complexes have a high productivity.
  • the transition metal complexes (A) and/or the iron complex (B) can therefore also optionally be immobilized on an organic or inorganic support (D) and be used in supported form in the polymerization. This enables, for example, deposits in the reactor to be avoided and the polymer morphology to be controlled.
  • silica gel magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polymers bearing polar functional groups, for example copolymers of ethene and acrylic esters, acrolein or vinyl acetate.
  • a catalyst system comprising at least one transition metal complex (A), at least one iron complex (B), at least one activating compound (C) and at least one support component (D).
  • the preferred catalyst composition according to the invention comprises one or more support components. It is possible for both the transition metal component (A) and the iron complex (B) to be supported, or only one of the two components can be supported. In a preferred embodiment, both the components (A) and (B) are supported.
  • the two components (A) and (B) can in this case be applied to different supports or together on a joint support.
  • the components (A) and (B) are preferably applied to a joint support in order to ensure a relatively close spatial proximity of the various catalyst centers and thus to ensure good mixing of the different polymers formed.
  • support component D transition metal complex (A), iron complex (B) and the activating compounds (C) are combined is in principle immaterial.
  • the various intermediates can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons.
  • Transition metal complex (A), iron complex (B) and the activating compound (C) can be immobilized independently of one another, e.g. in succession or simultaneously.
  • the support component (D) can firstly be brought into contact with the activating compound or compounds (C) or the support component (D) can firstly be brought into contact with the transition metal complex (A) and/or the iron complex (B).
  • Preactivation of the transition metal complex A) by means of one or more activating compounds (C) prior to mixing with the support (D) is also possible.
  • the iron component can, for example, be reacted simultaneously with the transition metal complex with the activating compound (C), or can be preactivated ' separately by means of the latter.
  • the preactivated iron complex (B) can be applied to the support before or after the preactivated transition metal complex (A).
  • the transition metal complex (A) and/or the iron complex (B) can also be prepared in the presence of the support material.
  • a further method of immobilization is prepolymerization of the catalyst system with or without prior application to a support.
  • the immobilization is generally carried out in an inert solvent which can be removed by filtration or evaporation after the immobilization.
  • the solid can be washed with suitably inert solvents such as aliphatic or aromatic hydrocarbons and dried.
  • suitably inert solvents such as aliphatic or aromatic hydrocarbons and dried.
  • the use of the still moist, supported catalyst is also possible.
  • At least one iron complex (B) is brought into contact with an activated compound (C) and subsequently mixed with the dehydrated or passivated support material (D).
  • the transition metal complex (A) is likewise brought into contact with at least one activating compound (C) in a suitable solvent, preferably giving a soluble reaction product, an adduct or a mixture.
  • the preparation obtained in this way is then mixed with .
  • the immobilized iron complex which is used directly or after the solvent has been separated off, and the solvent is completely or partly removed.
  • the resulting supported catalyst system is preferably dried to ensure that all or most of the solvent is removed from the pores of the support material.
  • the supported catalyst is preferably obtained as a free-flowing powder.
  • a further preferred embodiment comprises firstly producing the activating compound (C) on the support component (D) and subsequently bringing this supported compound into contact with the transition metal complex (A) and the iron complex (B).
  • the support component (D) preference is given to using finely divided supports which can be any organic or inorganic solid.
  • the support component (D) can be a porous support such as talc, a sheet silicate such as montmorillonite, mica or an inorganic oxide or a finely divided polymer powder (e.g. polyo ' lefin-or a polymer having polar functional groups).
  • the support materials used preferably have a specific surface area in the range from 10 to 1000 m 2 /g, a pore volume in the range from 0.1 to 5 mi/g and a mean particle size of from 1 to 500 ⁇ m. Preference is given to supports having a specific surface area in the range from 50 to 700 m 2 /g, a pore volume in the range from 0.4 to 3.5 ml/g and a mean particle size in the range from 5 to 350 ⁇ m.
  • the transition metal complex (A) is preferably applied in such an amount that the concentration of the transition metal from the transition metal complex (A) in the finished catalyst system is from 1 to 200 ⁇ mol, preferably from 5 to 100 ⁇ mol and particularly preferably from 10 to 70 ⁇ mol, per g of support (D).
  • the iron complex (B) is preferably applied in such an amount that the concentration of iron from, the iron complex (B) in the finished catalyst system is from 1 to 200 ⁇ mol, preferably from 5 to 100 ⁇ mol and particularly preferably from 10 to 70 ⁇ mol, per g of support (D).
  • the inorganic support can be subjected to a thermal treatment, e.g. to remove adsorbed water.
  • a thermal treatment is generally carried out at temperatures in the range from 50 to 1000°C, preferably from 100 to 600°C, with drying at from 100 to 200°C preferably being carried out under reduced pressure and/or under a blanket of inert gas (e.g. nitrogen), or the inorganic support can be calcined at temperatures of from 200 to 1000°C to produce the desired structure of the solid and/or set the desired OH concentration on the surface.
  • the support can also be treated chemically using customary dessicants such as metal alkyls preferably aluminum alkyls, chlorosilanes or SiCI 4 , or else methylaluminoxane. Appropriate treatment methods are described, for example, in WO 00/31090.
  • the inorganic support material can also be chemically modified.
  • treatment of silica gel with NH 4 SiF 6 or other fluorinating agents leads to fluorination of the silica gel surface
  • treatment of silica gels with silanes containing nitrogen-, fluorine- or sulfur-containing groups leads to correspondingly modified silica gel surfaces.
  • Organic support materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and are preferably likewise freed of adhering moisture, solvent residues or other impurities by appropriate purification and drying operations before use. It is also possible to use functionalized polymer supports, e.g. ones based on polystyrene, polyethylene, polypropylene or polybutylene, via whose functional groups, for example ammonium or hydroxy groups, at least one of the catalyst components can be immobilized. It is also possible to use polymer blends.
  • functionalized polymer supports e.g. ones based on polystyrene, polyethylene, polypropylene or polybutylene, via whose functional groups, for example ammonium or hydroxy groups, at least one of the catalyst components can be immobilized. It is also possible to use polymer blends.
  • Inorganic oxides suitable as support component (D) may be found among the oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
  • oxides preferred as supports include silicon dioxide, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and also corresponding oxide mixtures.
  • Other inorganic oxides which can be used alone or in combination with the abovementioned preferred oxidic supports are, for example, MgO, CaO, AIP0 4 , Zr0 2 , Ti0 2 , B 2 0 3 or mixtures thereof.
  • inorganic support materials are inorganic halides such as MgCI 2 or carbonates such as Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , sulfates such as Na 2 S0 4 , AI 2 (S0 4 ) 3 , BaS0 4 , nitrates ' such as KN0 3 , Mg(N0 3 ) 2 or AI(N0 3 ) 3 .
  • inorganic halides such as MgCI 2 or carbonates such as Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , sulfates such as Na 2 S0 4 , AI 2 (S0 4 ) 3 , BaS0 4 , nitrates ' such as KN0 3 , Mg(N0 3 ) 2 or AI(N0 3 ) 3 .
  • silica gels As solid support materials (D) for catalysts for olefin polymerization, preference is given to using silica gels since particles whose size and structure make them suitable as supports for olefin polymerization can be produced from thjs material.
  • Spray-dried silica gels which are spherical agglomerates of relatively small granular particles, i.e. primary particles, have been found to be particularly useful.
  • the silica gels can be dried and/or calcined before use.
  • hydrotalcites are a. natural mineral having the ideal formula Mg 6 AI 2 (OH) 16 C0 3 ' 4 H 2 0
  • Brucite crystallizes in a sheet structure with the metal ions in octahederal holes between two layers of close-packed hydroxyl ions, with only every second layer of the octahederal holes being occupied.
  • hydrotalcite some magnesium ions are replaced by aluminum ions, as a result of which the packet of layers gains a positive charge. This is balanced by the anions which are located together with water of crystallization in the layers in-between.
  • M(ll) is a divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and/or Fe and M(lll) is a trivalent metal such as Al, Fe, Co, Mn, La, Ce and/or Cr, x is a number from 0.5 to 10 in steps of 0.5, A is an interstitial anion and n is the charge on the interstitial anion which can be from 1 to 8, usually from 1 to 4, and z is an integer from 1 to 6, in particular from 2 to 4.
  • interstitial anions are organic anions such as alkoxide anions, alkyl ether sulfates, aryl ether sulfates or glycol ether sulfates, inorganic anions such as, in particular, carbonate, hydrogen carbonate, nitrate, chloride, sulfate or B(OH) 4 ⁇ or polyoxometal anions such as Mo 7 0 2 6" or V 10 O 28 6" .
  • organic anions such as alkoxide anions, alkyl ether sulfates, aryl ether sulfates or glycol ether sulfates
  • inorganic anions such as, in particular, carbonate, hydrogen carbonate, nitrate, chloride, sulfate or B(OH) 4 ⁇
  • polyoxometal anions such as Mo 7 0 2 6" or V 10 O 28 6" .
  • a mixture of a plurality of such anions is also possible.
  • hydrotalcites can be prepared from hydrotalcites by calcination, i.e. heating, by means of which, inter alia, the desired hydroxide group content can be set.
  • the preparation of the calcined hydrotalcites used according to the invention is usually carried out at temperatures above 180 ° C. Preference is given to calcination for a period of from 3 to 24 hours at temperatures of from 250 ° C to 10OO ' C, in particular from 400 ° C to 700 ° C. It is possible for air or inert gas to be passed over the solid or for a vacuum to be applied at the same time.
  • the natural or synthetic hydrotalcites firstly give off water, i.e. drying occurs.
  • the actual calcination the metal hydroxides are converted into the metal oxides by elimination of hydroxyl groups and interstitial anions; OH groups or interstitial anions such as carbonate can also still be present in the calcined hydrotalcites.
  • a measure of this is the loss on ignition. This is the weight loss experienced by a sample which is heated in two steps firstly for 30 minutes at 200 ° C in a drying oven and then for 1 hour at 950 ° C in a muffle furnace.
  • the calcined hydrotalcites used as component (D) are thus mixed oxides of the divalent and trivalent metals M(ll) and M(lll), with the molar ratio of M(ll) to M(lll) generally being in the range from 0.5 to 10, preferably from 0.75 to 8 and in particular from 1 to 4. Furthermore, normal amounts of impurities, for example Si, Fe, Na, Ca or Ti and also chlorides and sulfates, can also be present.
  • Preferred calcined hydrotalcites (D) are mixed oxides in which M(ll) is magnesium and M(lll) is aluminum.
  • Such aluminum-magnesium mixed oxides are obtainable from Condea Chemie GmbH (now Sasol Chemie), Hamburg under the trade name Puralox Mg.
  • Calcination i.e. transformation of the structure, can be confirmed, for example, by means of X-ray diffraction patterns.
  • the hydrotalcites, calcined hydrotalcites or silica gels used are generally used as finely divided powders having a mean particle diameter D50 of from 5 to 200 ⁇ m, preferably from 10 to 150 ⁇ m, particularly preferably from 15 to 100 ⁇ m and in particular from 20 to 70 ⁇ m, and usually have pore volumes of from 0.1 to 10 cm 3 /g, preferably from 0.2 to 5 cm 3 /g, and specific surface areas of from 30 to 1000 m 2 /g, preferably from 50 to 800 m 2 /g and in particular from 100 to 600 m 2 /g.
  • the transition metal complex (A) is preferably applied in such an amount that the concentration of the transition metal from the transition metal complex (A) in the finished catalyst system is from 1 to 100 ⁇ mol, preferably from 5 to 80 ⁇ mol and particularly preferably from 10 to 60 ⁇ mol, per g of support (D).
  • the catalyst system may further comprise, as additional component (E), a metal compound of the general formula (XX),
  • M G is Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc, in particular Li, Na, K, Mg, boron, aluminum or Zn,
  • R 1G ' is hydrogen, d-Cio-alkyl, C 6 -C 15 -aryl, alkylaryl or arylalkyl each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part,
  • R 2G and R 3G are each hydrogen, halogen, C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl or alkoxy each having from 1 to 20 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, or alkoxy together with C ⁇ -C 1Q -alkyl or C 6 -C 15 -aryl,
  • r G is an integer from 1 to 3
  • s G and t G are integers from 0 to 2, with the sum r G +s G +t G corresponding to the valence of ' M G ,
  • component (E) is usually not identical to the component (C). It is also possible to use mixtures of various metal compounds of the formula (XX).
  • R 1G is C,-C 20 -alkyi.
  • Particularly preferred metal compounds of the formula (XX) are methyllithium, ethyllithium, n-butyllithium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesiUm, n-butyl-n-octylmagnesium, n-butyl-n-heptylmagnesium, in particular n-butyl-n-octylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, tri-n-butylaluminum, triethylaluminum, dimethylaluminum chloride, dimethylaluminum fluoride, methylaiuminum dichloride, methylaiuminum sesquichloride, diethylaluminum chlor
  • a metal compound (E) When a metal compound (E) is used, it is preferably present in the catalyst system. in such an amount that the molar ratio of M G from formula (XX) to the sum of the transition metals from the transition metal complex (A) and the iron complex (B) is from 3000:1 to 0.1 :1 , preferably from 800:1 to 0.2:1 and particularly preferably from 100:1 to 1 :1.
  • the metal compound (E) of the general formula (XX) is used as constituent of a catalyst system for the polymerization or copolymerization of olefins.
  • the metal compound (E) can, for example, be used for preparing a catalyst solid comprising the support (D) and/or be added during or shortly before the polymerization.
  • the metal compounds (E), used can be identical or different. It is also possible, particularly when the catalyst solid contains no activating component (C), for the catalyst system to further comprise, in addition to the catalyst solid, one or more activating compounds (C) which are identical to or different from any compounds (E) present in the catalyst solid.
  • the component E) can likewise be reacted in any order with the components (A), (B) and optionally (C) and (D).
  • the component (A) can, for example, be brought into contact with the component(s) (C) and/or (D) either before or after being brought into contact with the olefins to be polymerized.
  • Preactivation by means of one or more components (C) prior to mixing with the olefin and further addition of the same or another component (C) and/or (D) after this mixture has been brought into contact with the olefin is also possible. Preactivation is generally carried out at temperatures of 10-100°C, preferably 20-80°C. ,
  • a catalyst solid is prepared from the components (A), (B), (C) and (D) as described above and this is brought into contact with the component (E) during, at the commencement of or shortly before the polymerization.
  • the support (D) is firstly brought into contact with the . component (E), and the components (A) and (B) and any further activator (C) are then dealt with as described above.
  • the catalyst system firstly to be prepolymerized with -olefins, preferably linear C 2 -C 10 -1-alkenes and in particular ethylene or propylene, and the resulting prepolymerized catalyst solid then to be used in the actual polymerization.
  • -olefins preferably linear C 2 -C 10 -1-alkenes and in particular ethylene or propylene
  • the mass ratio of catalyst solid used in the prepolymerization to a monomer polymerized onto it is usually in the range from 1 :0.1 to 1 :1000,. preferably from 1 :1 to 1 :200.
  • an olefin preferably an ⁇ -olefin, for example vinylcyclohexane, styrene or phenyldimethylvinylsiiane
  • an antistatic or a suitable inert compound such as a wax or oil
  • the molar ratio of additives to the sum of transition metal compound (A) and. iron complex (B) is usually from 1 :1000 to 1000:1 , preferably from 1 :5 to 20:1.
  • the catalyst composition or catalyst system of the invention is suitable for preparing the polyethylene of the invention, which has advantageous use and processing properties.
  • the ethylene is polymerized as described above with 1-alkenes having from 3 to 10 carbon atoms.
  • ethylene is polymerized with 1-alkenes having from 3 to 12 carbon atoms.
  • Preferred 1-alkenes are linear or branched C 2 -C 10 -1-alkehes, in particular linear C 2 -C 8 -1-alkenes such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or branched C 2 -C 10 -1-alkenes such as 4-methyl-1-pentene.
  • Particularly preferred 1-alkenes are C 4 -C 10 -1-alkenes, in particular linear C 6 -C 10 -1-alkenes.
  • polymerize mixtures of various 1-alkenes Preference is given to polymerizing at least one 1-alkene selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene. Monomer mixtures containing at least 50 mol% of ethene are preferably used.
  • the process of the invention for polymerizing ethylene with 1-alkenes can be carried out using all industrially known polymerization methods at temperatures in the range from -60 to 350°C, preferably from 0 to 200°C and particularly preferably from 25 to 150°C, and under pressures of from 0.5 to 4000 bar, preferably from 1 to 100 bar and particularly preferably from 3 to 40 bar.
  • the polymerization can be carried out in a known manner in bulk, in suspension, in the gas phase or in a supercritical medium in the customary reactors used for the polymerization of olefins. It can be carried out batchwise or preferably continuously in one or more stages. High-pressure polymerization processes in tube reactors or autoclaves, solution processes, suspension processes, stirred gas-phase processes and gas-phase fluidized-bed processes are all possible.
  • the polymerizations are usually carried out at temperatures in the range from -60 to 350°C, preferably in the range from 20 to 300°C, and under pressures of from 0.5 to 4000 bar.
  • the mean residence times are usually from 0.5 to 5 hours, -preferably from 0.5 to 3 hours.
  • the advantageous pressure and temperature ranges for carrying out the polymerizations usually depend on the polymerization method. In the case of high-pressure polymerization processes, which are customarily carried out at pressures of from 1000 to 4000 bar, in particular from 2000 to 3500 bar, high polymerization temperatures are generally also set.
  • Advantageous temperature ranges for these high-pressure polymerization processes are from 200 to 320°C, in particular from 220 to 290°C.
  • a temperature which is at least a few degrees below the softening temperature of the polymer. In particular, temperatures of from 50 to 180°C, preferably from 70 to 120°C, are set in these polymerization processes.
  • the polymerization is usually carried out in a suspension medium, preferably an inert hydrocarbon such as isobutane or mixtures of hydrocarbons or else in the monomers themselves.
  • the polymerization temperatures are generally in the range from -20 to 115°C, and the pressure is generally in the range from 1 to 100 bar.
  • the solids content of the suspension is generally in the range from 10 to 80%.
  • the polymerization can be carried out either batchwise, e.g.
  • the gas-phase polymerization is generally carried out in the range from 30 to 125°C at pressures of from 1 to 50 bar.
  • gas- phase polymerization in particular in gas-phase fluidized-bed reactors, solution polymerization and suspension polymerization, in particular in loop reactors and stirred tank reactors.
  • the gas- phase polymerization can also be carried out in the condensed or supercondensed mode, in which part of the circulating gas is cooled to below the dew point and is recirculated as a two- phase mixture to the reactor.
  • the two zones can also have different polymerization conditions.
  • Such a reactor is described, for example, in WO 97/04015.
  • the different or identical polymerization processes can also, if desired, be connected in series so as to form a polymerization cascade, for example as in the Hostalen® process.
  • a parallel reactor arrangement using two or more identical or different processes is also possible.
  • molar mass regulators for example hydrogen, or customary additives such as antistatics can also be used in the polymerizations.
  • Hydrogen can especially be used to enhance the activity of the hafnocene (A).
  • the hydrogen and increased temperature usually lead to lower z-average molar mass.
  • the polymerization is preferably carried out in a single reactor, in particular in a gas-phase reactor.
  • the polymerization of ethylene with 1-alkenes having from 3 to 10 carbon atoms gives the polyethylene of the invention when the catalyst of the invention is used.
  • the polyethylene powder obtained directly from the reactor displays a very high homogeneity, so that, unlike the case of cascade processes, subsequent extrusion is not necessary in order to obtain a homogeneous product.
  • the production of polymer blends by intimate mixing of individual components, for example by melt extrusion in an extruder or kneader (cf., for example, "Polymer Blends" in Uilmann's Encyclopedia of Industrial Chemistry, 6 th Edition, 1998, Electronic Release), is often accompanied by particular difficulties.
  • melt viscosities of the high and low molecular weight components of a bimodal polyethylene blend are extremely different. While the low molecular weight component is quite fluid at the customary temperatures of about 190-210°C used for producing the blends, the high molecular weight component is only softened ("lentil soup"). Homogeneous mixing of the two components is therefore for very difficult. In addition, it is known that the high molecular weight component can easily be damaged as a result of thermal stress and by shear forces in the extruder, so that the properties of the blend are adversely affected. The mixing quality of such polyethylene blends is therefore often unsatisfactory.
  • the mixing quality of the polyethylene powder obtained directly from the reactor can be tested by assessing thin slices ("microtome sections") of a sample under an optical microscope. Inhomogenities show up in the form of specks or "white spots".
  • the specs or "white spots” are predominantly high molecular weight, high-viscosity particles in a low-viscosity matrix (cf., for example, U. Burkhardt et al. in " Aufleen von Polymeren mit neuartigen yoga", VDI r Verlag, D ⁇ sseldorf 1995, p. 71 ).
  • Such inclusions can reach a size of up to 300 ⁇ m, cause stress cracks and result in brittle failure of components.
  • the mixing quality of a polymer is determined quantitatively in accordance with ISO 13949. According to the measurement method, a microtome section is prepared from a sample of the polymer, the number and size of these inclusions are counted and a grade is determined for the mixing quality of the polymer according to a set assessment scheme.
  • the mixing quality of the polyethylene of the inevtion, obtained directly from the reactor is preferably below 3.
  • the preparation of the polyethylene of the invention in the reactor reduces the energy consumption, requires no subsequent blending processes and makes simple control of the molecular weight distributions and the molecular weight fractions of the various polymers possible. In addition, good mixing of the polyethylene is achieved.
  • the vinyl group content is determined by means of IR in accordance with ASTM D 6248-98.
  • the branches/1000 carbon atoms are determined by means of 13 C-NMR, as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989), and are based on the total content of CH 3 groups/1000 carbon atoms.
  • the side chains larger than CH 3 and especially ethyl, butyl and hexyl side chain branches/1000 carbon atoms are likewise determined in this way.
  • the degree of branching in the individual polymer fractions is determined by the method of Holtrup (W. Holtrup, Makromol. Chem. 178, 2335 (1977)) coupled with 13 C-NMR.
  • the density [g/cm 3 ] was determined in accordance with ISO 1183.
  • the columns were calibrated with polyethylene standards with molar masses of from 100 bis 10 7 g/mol.
  • the evaluation was carried out by using the Win-GPC software of Fa. HS-Entwicklungsgesellschaft fur letone Hard- und Software mbH, Ober-Hilbersheim.
  • HLMI refers, as is generally known, to the “high load melt flow rate” and is always determined at 190°C under a load of 21.6 kg (190°C/21.6 kg) in accordance with ISO 1133.
  • the haze was determined by ASTM D 1003-00 on a BYK Gardener Haze Guard Plus Device on at least 5 pieces of film 10x10 cm with a thickness of 50 ⁇ m.
  • the dart drop was determined by ASTM D 1709 Method A on a film with a thickness of 50 ⁇ m.
  • the clarity was determined by ASTM D 1746 - 03 on a BYK Gardener Haze Guard Plus Device, calibrated with calibration cell 77.5, ' on at least 5 pieces of film 10x10 cm with a thickness of 50 ⁇ m.
  • the gloss 45° was determined by ASTM D 2457 -03 on a gloss meter 45° with a vacuum plate for fixing the film, on at least 5 pieces" of film with a thickness of 50 ⁇ m.
  • GPC % at molar mass 1 Mio is the % by weight according to gel permeation chromatography below a molar mass of 1 Mio g/mol.
  • Bis(n-butylcyclopentadienyl)hafnium dichloride is commercially available from Crompton.
  • 2,6-Bis[1-(2-tert.butyiphenylimino)ethyl]pyridine was prepared as in example 6 of WO 98/27124 and 2,6-Bis[1-(2-tert.butylphenylimino)ethyl]pyridine iron(ll) dichloride was prepared as in example 15 of WO 98/27124.
  • XPO-2107 a spray-dried silica gel from Grace, was baked at 600°C for 6 hours.
  • XPO-2107 a spray-dried silica gel from Grace, was baked at 600°C for 6 hours.
  • the suspension was filtrated and washed with 500 ml of toluene.
  • the residual solid was dried under reduced pressure until it was free-flowing powder.
  • the catalyst still contained 25.2 %. by weight of solvent (based on the total weight and calculated on the basis of complete application of all components to the support).
  • Comparative Example C1 a) Support pretreatment XPO-2107, a spray-dried silica gel from Grace, was baked at 600°C for 6 hours. b) Preparation of the mixed catalyst systems
  • XPO-2107 a spray-dried silica gel from Grace, was baked at 600°C for.6 hours.
  • the polymerization was carried out in a fluidized-bed reactor having . a diameter of 0.5 m.
  • the reaction temperature, output and the composition of the reactor gas are reported in Table 1 , and the pressure in the reactor was 20 bar.
  • 0.1 g of triisobutylaluminum per hour were metered in in each case.
  • Catalysts employed were the catalysts from the examples.
  • the properties of the polymers obtained are summarized in Table 2.
  • the obtained polyethylenes were homogenised and granulated on a ZSK 30 (Werner Pfleiderer) with screw combination 8A.
  • the processing temperature was 220 °C, the screw speed 250/min with maximum output at 20 kg/h. 1500 ppm Irganox B215 were added to stabilize the polyethylenes.
  • the polymer was extruded into films by blown film extrusion on a Weber film extruder equipped with a collapsing device with wooden flatted boards.
  • the diameter of the ring die was 50 mm, the gap width was 2/50 and the angel in which the cooling air is blown onto the extruded film is 45°. No filters were used.
  • the blow-up ratio was 1 :2 and ist the haul-off speed 4.9 m/10 min.
  • the height of the frost line was 160 mm. Films with a thickness of 50 ⁇ m were obtained.
  • Table 3 The processing properties and optical and mechanical properties of the films are summarized in Table 3.
  • Tabel 3 Processing properties and optical and mechanical properties of the films

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Families Citing this family (142)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE602004019967D1 (de) * 2003-12-16 2009-04-23 Basell Polyolefine Gmbh Monocyclopentadienylkomplexe
JP2007514685A (ja) * 2003-12-19 2007-06-07 バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング モノシクロペンタジエニル錯体
EP1559728A1 (de) * 2004-01-28 2005-08-03 Total Petrochemicals Research Feluy Pfropfung von Übergangsmetallkomplexen auf Trägern
DE102004020524A1 (de) 2004-04-26 2005-11-10 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung zu dessen Herstellung
DE102004029465A1 (de) 2004-06-18 2006-01-05 Basell Polyolefine Gmbh Verfahren zur Bestimmung und Regelung der Zusammensetzung von Polymermischungen bei der Polymerisation
EP1650231A1 (de) * 2004-10-21 2006-04-26 Total Petrochemicals Research Feluy Polyolefine hergestellt mit Metallocen- und neuen Single-Site-Katalysatorkomponenten in einem Reaktor
DE102005019393A1 (de) 2005-04-25 2006-10-26 Basell Polyolefine Gmbh Polyethylenformmassen für Spritzgussanwendungen
DE102005019395A1 (de) * 2005-04-25 2006-10-26 Basell Polyolefine Gmbh Formmasse aus Polyethylen zur Folienherstellung und Verfahren zum Herstellen der Formmasse in Gegenwart eines Mischkatalysators
EP1716924A1 (de) * 2005-04-29 2006-11-02 Saudi Basic Industries Corporation Katalysatorvorläufer für die Herstellung von Olefinen mit ungerader Anzahl von Kohlenstoffatomen, Verfahren zu seiner Herstellung und Verfahren zur Herstellung derartiger Olefine
BRPI0611231A2 (pt) * 2005-05-10 2010-08-24 Ineos Europe Ltd copolÍmero de etileno e uma alfa-olefina, mÉtodo para a preparaÇço de copolÍmeros, artigo rotomodulado e uso de um copolÍmero preparado pelo uso de um componente de catalisador de monociclopentadienil metaloceno
US7078467B1 (en) * 2005-06-14 2006-07-18 Univation Technologies, Llc Single catalyst low, medium and high density polyethylenes
US7723448B2 (en) * 2005-10-14 2010-05-25 Basell Polyolefine Gmbh Hybrid catalyst systems supported on magnesium halide
RU2008126259A (ru) 2005-11-28 2010-01-10 Базелль Полиолефине Гмбх (De) Полиэтиленовая композиция, пригодная для получения пленок, и способ их получения
US7595364B2 (en) 2005-12-07 2009-09-29 Univation Technologies, Llc High density polyethylene
EP1969022B1 (de) * 2005-12-29 2011-03-02 Dow Global Technologies Inc. Niedermolekulare ethylen-mischpolymere, herstellungsverfahren dafür und verwendungen davon
DE102006001959A1 (de) 2006-01-13 2007-07-19 Basell Polyolefine Gmbh Verfahren zur Herstellung von unsymmetrischen Bis(imino)verbindungen
AU2007211671A1 (en) * 2006-01-31 2007-08-09 Basell Polyolefine Gmbh Copolymers of ethylene and at least one other 1-olefin, and process for their preparation
CA2648470C (en) 2006-04-07 2014-09-16 Dow Global Technologies Inc. Polyolefin compositions, articles made therefrom and methods for preparing the same
US8247065B2 (en) 2006-05-31 2012-08-21 Exxonmobil Chemical Patents Inc. Linear polymers, polymer blends, and articles made therefrom
EP2102282B1 (de) * 2006-12-22 2011-02-09 Basell Polyolefine GmbH Multimodale polyethylenzusammensetzung, mischkatalysaotr und verfahren zur herstellung der zusammensetzung
US10626202B2 (en) * 2007-02-01 2020-04-21 Basell Polyolefine Gmbh Monomodal copolymer of ethylene for injection molding and process for its preparation
JP5462634B2 (ja) 2007-03-06 2014-04-02 バーゼル・ポリオレフィン・ゲーエムベーハー 鉄コンプレックス及び重合プロセスにおけるそれらの使用
DE102007017903A1 (de) 2007-04-13 2008-10-16 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung und Verfahren zu dessen Herstellung
US20100093953A1 (en) * 2007-05-04 2010-04-15 Basell Polyolefine Gmbh Polyethylene, process and catalyst composition for the preparation thereof
EP2003166A1 (de) * 2007-06-12 2008-12-17 Repsol Ypf S.A. Polyethylenzusammensetzungen und ihre Verwendung bei der Herstellung von Röhren
CN101981110B (zh) * 2007-12-18 2013-03-27 巴塞尔聚烯烃股份有限公司 生产注塑螺帽盖子的pe模塑组合物和用其生产的用于充碳酸气的饮料的高强度螺帽盖子
CN101903418A (zh) * 2007-12-21 2010-12-01 巴塞尔聚烯烃股份有限公司 包含菲咯啉的络合物
WO2009080237A1 (en) * 2007-12-21 2009-07-02 Basell Polyolefine Gmbh Catalyst sytem for olefin polymerization comprising phenantroline-comprising iron complexes
WO2009080359A1 (en) 2007-12-24 2009-07-02 Basell Polyolefine Gmbh Multistage process for the polymerization of olefins
WO2009085922A1 (en) * 2007-12-31 2009-07-09 Dow Global Technologies Inc. Ethylene-based polymer compositions, methods of making the same, and articles prepared from the same
EP2236577A3 (de) 2008-02-18 2011-05-04 Basell Polyolefine GmbH Polyäthylenartikel
KR100976666B1 (ko) * 2008-07-21 2010-08-18 대림산업 주식회사 올레핀 중합 촉매 및 이를 이용한 폴리올레핀 중합체의제조방법
CN102105497B (zh) 2008-07-23 2016-02-24 巴塞尔聚烯烃股份有限公司 不相容烯烃聚合催化剂体系之间转变的方法
US7973116B2 (en) * 2008-07-25 2011-07-05 Exxonmobil Chemical Patents Inc. Pyridyldiamido transition metal complexes, production and use thereof
CN102197081B (zh) * 2008-08-29 2013-08-21 巴塞尔聚烯烃股份有限公司 注塑用聚乙烯
CN102164992A (zh) * 2008-09-25 2011-08-24 巴塞尔聚烯烃股份有限公司 抗冲击的lldpe组合物和由其制备的薄膜
EP2344551B1 (de) * 2008-09-25 2014-05-28 Basell Polyolefine GmbH Schlagzähe lldpe-zusammensetzungen und daraus hergestellte folien
WO2010034463A1 (en) * 2008-09-25 2010-04-01 Basell Polyolefine Gmbh Impact resistant lldpe composition and films made thereof
US20110212315A1 (en) * 2008-09-25 2011-09-01 Basell Polyolefine Gmbh Impact Resistant LLDPE Composition and Films Made Thereof
US8435911B2 (en) * 2008-10-16 2013-05-07 Basell Polyolefine Gmbh Hybrid catalyst composition for polymerization of olefins
US8715813B2 (en) 2008-10-23 2014-05-06 Exxonmobil Chemical Patents Inc. High MIR linear polyethylenes and coextruded films therefrom
US8022154B2 (en) * 2008-11-06 2011-09-20 Exxonmobil Chemical Patents Inc. Ethylene polymers, their production and use
CN102257014B (zh) * 2008-12-17 2014-06-04 巴塞尔聚烯烃股份有限公司 用于烯烃聚合的催化剂体系、它的生产和用途
SG171988A1 (en) 2008-12-23 2011-07-28 Basell Polyolefine Gmbh Method for transitioning between incompatible olefin polymerization catalyst systems
JP2012515239A (ja) * 2009-01-13 2012-07-05 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ ポリマー組成物
US8907035B2 (en) 2009-01-13 2014-12-09 Basell Polyolefine Gmbh Polyethylene Copolymers
US8569434B2 (en) 2009-02-20 2013-10-29 Basell Polyolefine Gmbh Ethylene copolymers, catalyst system and process for preparing the same
ES2487517T3 (es) 2009-05-26 2014-08-21 Borealis Ag Composición polimérica para artículos reticulados
EP2256159A1 (de) 2009-05-26 2010-12-01 Borealis AG Polymerzusammensetzung für vernetzte Rohre
US8471050B2 (en) 2009-07-27 2013-06-25 Basell Polyolefine Gmbh Organometallic transition metal compound, catalyst system and preparation of polyolefins
CN102482377A (zh) * 2009-08-21 2012-05-30 巴塞尔聚烯烃股份有限公司 用于旋转注模的聚乙烯
WO2011020622A1 (en) 2009-08-21 2011-02-24 Basell Polyolefine Gmbh Polyethylene for rotomoulding
WO2011020621A1 (en) 2009-08-21 2011-02-24 Basell Polyolefine Gmbh Polyethylene for rotomoulding
CN102712715B (zh) * 2010-01-21 2014-10-29 巴塞尔聚烯烃股份有限公司 在低聚催化剂存在下制备乙烯共聚物组合物的方法
PL2563957T3 (pl) * 2010-04-30 2018-09-28 Basell Polyolefine Gmbh Polimerowy filament lub włókno
CN103347910B (zh) 2010-12-22 2016-01-20 巴塞尔聚烯烃股份有限公司 控制包含至少一种后过渡金属催化剂组分和至少一种Ziegler催化剂组分的催化剂体系的活性中心的相对活性的工艺
JP5714957B2 (ja) * 2011-03-29 2015-05-07 住友化学株式会社 オレフィン重合体の製造方法
JP5986630B2 (ja) 2011-07-05 2016-09-06 ダウ グローバル テクノロジーズ エルエルシー エチレン系ポリマーおよびそれを作製する方法
US9371442B2 (en) 2011-09-19 2016-06-21 Nova Chemicals (International) S.A. Polyethylene compositions and closures made from them
CA2752407C (en) 2011-09-19 2018-12-04 Nova Chemicals Corporation Polyethylene compositions and closures for bottles
US9321945B2 (en) 2011-09-30 2016-04-26 Equistar Chemicals, Lp Systems, methods and compositions for production of tie-layer adhesives
EP2751189B1 (de) * 2011-09-30 2015-09-30 Total Research & Technology Feluy Hochdichtes polyethylen für deckel und verschlüsse
US9023967B2 (en) * 2011-11-30 2015-05-05 Chevron Phillips Chemical Company Lp Long chain branched polymers and methods of making same
EP2607391A1 (de) 2011-12-21 2013-06-26 Basell Polyolefine GmbH Verfahren zur Steuerung der Polymerzusammensetzung eines Ethylen-Copolymers, das von einem Katalysator-System, umfassend eine Übergangsmetall-Katalysatorkomponente und eine Ziegler-Katalysatorkomponente, erhalten wird
GB2498936A (en) 2012-01-31 2013-08-07 Norner Innovation As Polyethylene with multi-modal molecular weight distribution
KR101975078B1 (ko) 2012-06-01 2019-05-03 다우 글로벌 테크놀로지스 엘엘씨 알킬화된 페놀을 사용하여 에틸렌계 중합체를 제조하기 위한 자유-라디칼 방법
JP6165853B2 (ja) * 2012-06-11 2017-07-19 ユニリーバー・エヌ・ブイ 高密度ポリエチレン組成物およびクロージャ
US10465021B2 (en) * 2012-07-27 2019-11-05 Fina Technology, Inc. Uncompounded particulate metallocene-produced polyethylene
MX2015003370A (es) 2012-09-13 2015-06-05 Dow Global Technologies Llc Composiciones polimericas a base de etileno y articulos preparados a partir de las mismas.
EP2743000A1 (de) 2012-12-13 2014-06-18 Basell Poliolefine Italia S.r.l. Katalysatorsystem zur Herstellung von Polyolefinen
US9783663B2 (en) 2012-12-14 2017-10-10 Nova Chemicals (International) S.A. Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
CA2798854C (en) 2012-12-14 2020-02-18 Nova Chemicals Corporation Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
US9475927B2 (en) 2012-12-14 2016-10-25 Nova Chemicals (International) S.A. Polyethylene compositions having high dimensional stability and excellent processability for caps and closures
BR112015026566A2 (pt) * 2013-05-02 2017-07-25 Dow Global Technologies Llc composição de polietileno, artigo e película
US9441062B2 (en) 2013-05-09 2016-09-13 Abu Dhabi Polymers Company Limited (Borouge), Llc Multimodal polyethylene polymers and methods of making and using the same
CN105358586A (zh) 2013-07-17 2016-02-24 埃克森美孚化学专利公司 环丙基取代的茂金属催化剂
US9458254B2 (en) 2013-07-17 2016-10-04 Exxonmobil Chemical Patents Inc. Substituted metallocene catalysts
EP3301119B1 (de) 2013-07-17 2021-03-17 ExxonMobil Chemical Patents Inc. Isotaktische propylenpolymere
EP3022237B1 (de) 2013-07-17 2018-10-03 ExxonMobil Chemical Patents Inc. Metallocene und katalysatorzusammensetzungen daraus
US9938364B2 (en) 2013-07-17 2018-04-10 Exxonmobil Chemical Patents Inc. Substituted metallocene catalysts
WO2015009470A1 (en) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
RU2677461C2 (ru) * 2013-10-14 2019-01-17 Базелл Полиолефин Гмбх Состав полиэтилена повышенной температурной устойчивости
WO2015055393A1 (en) 2013-10-15 2015-04-23 Basell Polyolefine Gmbh Polyethylene for injection moulding
KR101813418B1 (ko) 2013-10-15 2017-12-28 바젤 폴리올레핀 게엠베하 사출 성형용 폴리에틸렌 조성물
US20150322184A1 (en) * 2014-05-07 2015-11-12 Chevron Phillips Chemical Company Lp High Performance Moisture Barrier Films at Lower Densities
US9079993B1 (en) 2014-05-22 2015-07-14 Chevron Phillips Chemical Company Lp High clarity low haze compositions
EP3186311B1 (de) 2014-08-29 2023-07-19 Dow Global Technologies LLC Ethylenbasierte harze für schliessanwendungen
BR102015027108B1 (pt) 2014-10-27 2021-01-12 China Petroleum & Chemical Corporation composição de polietileno, e, película
CN105524337B (zh) * 2014-10-27 2018-04-10 中国石油化工股份有限公司 一种聚乙烯组合物及其薄膜
CN107428863B (zh) * 2015-03-31 2020-03-06 日本聚乙烯株式会社 管与接头用聚乙烯、及其成形体
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
EP3885373A1 (de) 2015-06-05 2021-09-29 ExxonMobil Chemical Patents Inc. Herstellung von heterophasischen polymeren in gas- oder schlämmephase
WO2016196331A1 (en) 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
CN107690441A (zh) 2015-06-05 2018-02-13 埃克森美孚化学专利公司 聚合物在气相或淤浆相中的单反应器制备
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US9809664B2 (en) 2015-06-05 2017-11-07 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US9758653B2 (en) 2015-08-19 2017-09-12 Nova Chemicals (International) S.A. Polyethylene compositions, process and closures
US10213766B2 (en) 2015-09-18 2019-02-26 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst
EP3739088A1 (de) * 2015-12-15 2020-11-18 DSM IP Assets B.V. Faser mit geringem kriechfaktor
ES2691556T5 (es) 2016-03-02 2022-09-29 Dow Global Technologies Llc Una composición de un copolímero de etileno/alfa-olefina, y artículos que comprenden la misma
CN109312013A (zh) 2016-05-27 2019-02-05 埃克森美孚化学专利公司 茂金属催化剂组合物和使用其的聚合方法
US9783664B1 (en) 2016-06-01 2017-10-10 Nova Chemicals (International) S.A. Hinged component comprising polyethylene composition
EP3778666B1 (de) 2016-11-08 2023-12-13 Univation Technologies, LLC Polyethylenzusammensetzung
KR102433606B1 (ko) 2016-11-08 2022-08-22 유니베이션 테크놀로지즈, 엘엘씨 폴리에틸렌 조성물
US10000594B2 (en) 2016-11-08 2018-06-19 Chevron Phillips Chemical Company Lp Dual catalyst system for producing LLDPE copolymers with a narrow molecular weight distribution and improved processability
EP3415540B1 (de) 2016-11-15 2022-09-14 LG Chem, Ltd. Ethylen/alpha-olefin-copolymer mit hervorragender spannungsrissbeständigkeit
KR102072697B1 (ko) * 2016-12-09 2020-02-03 주식회사 엘지화학 가공성 및 기계적 물성이 우수한 에틸렌/1-헥센 공중합체
US20200369803A1 (en) 2016-12-29 2020-11-26 Chevron Phillips Chemical Company Lp Methods of Preparing a Catalyst
US11267914B2 (en) 2016-12-29 2022-03-08 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst
US10654953B2 (en) 2016-12-29 2020-05-19 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst
US10287369B2 (en) 2017-04-24 2019-05-14 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst
CN111051419A (zh) 2017-09-11 2020-04-21 尤尼威蒂恩技术有限责任公司 含有碳黑的双峰聚乙烯组合物
WO2019099117A1 (en) * 2017-11-14 2019-05-23 Exxonmobil Chemical Patents Inc. Iron tridentate carbene single site catalysts
US10513570B2 (en) 2017-11-17 2019-12-24 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst
US10323109B2 (en) 2017-11-17 2019-06-18 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst utilizing hydrated reagents
WO2019108977A1 (en) * 2017-12-01 2019-06-06 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same
WO2019121234A1 (en) * 2017-12-18 2019-06-27 Basell Polyolefine Gmbh Polyethylene composition having environmental stress cracking resistance
JP6950566B2 (ja) * 2018-02-20 2021-10-13 日本ポリエチレン株式会社 架橋ポリエチレン管用ポリエチレン樹脂組成物、及び、架橋ポリエチレン管
BR112020018814B1 (pt) 2018-03-28 2023-12-12 Univation Technologies, Llc Composição de polietileno bimodal, método para produzir uma composição de polietileno bimodal, artigo fabricado e tampa ou fecho de garrafa
US10543480B2 (en) 2018-04-16 2020-01-28 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst utilizing hydrated reagents
US11266976B2 (en) 2018-04-16 2022-03-08 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst with low HRVOC emissions
US10722874B2 (en) 2018-04-16 2020-07-28 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst utilizing hydrated reagents
KR102165484B1 (ko) * 2018-05-10 2020-10-14 한화솔루션 주식회사 올레핀 중합 촉매용 전이금속 화합물 및 이를 포함하는 올레핀 중합 촉매
JP2021529227A (ja) * 2018-06-28 2021-10-28 ダウ グローバル テクノロジーズ エルエルシー 改善された溶融強度および熱安定性を有するエチレン系ポリマー
CA3028148A1 (en) 2018-12-20 2020-06-20 Nova Chemicals Corporation Polyethylene copolymer compositions and articles with barrier properties
WO2020169423A1 (en) 2019-02-20 2020-08-27 Basell Polyolefine Gmbh Extrusion additive manufacturing process for producing polyethylene articles
WO2020247192A1 (en) 2019-05-24 2020-12-10 Eastman Chemical Company Recycle content cracked effluent
EP3976732A4 (de) 2019-05-24 2023-05-17 Eastman Chemical Company Mischung von kleinen mengen von pyrolyseöl zu einem flüssigkeitsstrom, der zu einen gas-cracker verarbeitet wird
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers
US11945998B2 (en) 2019-10-31 2024-04-02 Eastman Chemical Company Processes and systems for making recycle content hydrocarbons
WO2021092306A1 (en) 2019-11-07 2021-05-14 Eastman Chemical Company Recycle content alpha olefins and fatty alcohols
WO2021092305A1 (en) 2019-11-07 2021-05-14 Eastman Chemical Company Recycle content mixed esters and solvents
EP4077422A1 (de) * 2019-12-17 2022-10-26 ExxonMobil Chemical Patents Inc. Polyethylene mit breiter orthogonaler verteilung für filme
WO2021195505A1 (en) 2020-03-27 2021-09-30 Dow Global Technologies Llc Long-chain branched ethylene-based polymers
CN115397875A (zh) * 2020-03-27 2022-11-25 陶氏环球技术有限责任公司 用于产生长链支化基于乙烯的聚合物的方法
KR20220158825A (ko) 2020-04-01 2022-12-01 다우 글로벌 테크놀로지스 엘엘씨 바이모달 선형 저밀도 폴리에틸렌 공중합체
WO2022076216A1 (en) 2020-10-08 2022-04-14 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
US11674023B2 (en) * 2020-10-15 2023-06-13 Chevron Phillips Chemical Company Lp Polymer composition and methods of making and using same
US11578156B2 (en) 2020-10-20 2023-02-14 Chevron Phillips Chemical Company Lp Dual metallocene polyethylene with improved processability for lightweight blow molded products
JP2024537225A (ja) 2021-10-28 2024-10-10 バーゼル・ポリオレフィン・ゲーエムベーハー 強化ポリプロピレン組成物

Family Cites Families (135)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL109815C (de) 1955-07-29 1900-01-01
US3242150A (en) * 1960-03-31 1966-03-22 Phillips Petroleum Co Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone
US3125547A (en) 1961-02-09 1964-03-17 Extrudable composition consisting of
US3248179A (en) 1962-02-26 1966-04-26 Phillips Petroleum Co Method and apparatus for the production of solid polymers of olefins
IT1098272B (it) 1978-08-22 1985-09-07 Montedison Spa Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine
US4438238A (en) * 1981-01-30 1984-03-20 Sumitomo Chemical Company, Limited Low density copolymer composition of two ethylene-α-olefin copolymers
US4461873A (en) 1982-06-22 1984-07-24 Phillips Petroleum Company Ethylene polymer blends
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US5580939A (en) 1983-06-06 1996-12-03 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
ZA844157B (en) 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
US4577768A (en) 1983-11-03 1986-03-25 Owens-Illinois, Inc. Ethylene polymer blend and containers prepared therefrom
US7163907B1 (en) 1987-01-30 2007-01-16 Exxonmobil Chemical Patents Inc. Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization
US5055438A (en) 1989-09-13 1991-10-08 Exxon Chemical Patents, Inc. Olefin polymerization catalysts
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
US5382630A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution
KR0122879B1 (ko) 1988-09-30 1997-11-12 존 제이.마흔 좁은 분자량 및 조성 분포를 갖는 인터폴리머의 선형 에틸렌 인터폴리머 블렌드
NZ235032A (en) 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
IL96810A0 (en) 1990-01-02 1991-09-16 Exxon Chemical Patents Inc Supported ionic metallocene catalysts for olefin polymerization and methods for the preparation thereof
AU660043B2 (en) 1991-07-18 1995-06-08 Exxon Chemical Patents Inc. Heat sealed article
KR930006090A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 에틸렌 중합체 조성물
KR930006091A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 폴리에틸렌 블렌드 및 그로부터 제조된 필름, 병 또는 파이프
KR930006089A (ko) 1991-09-18 1993-04-20 제이 이이 휘립프스 폴리에틸렌 블렌드
CA2078366A1 (en) 1991-09-18 1993-03-19 Joel L. Martin Polyethylene blends
TW309523B (de) * 1991-11-30 1997-07-01 Hoechst Ag
US5530065A (en) 1992-01-07 1996-06-25 Exxon Chemical Patents Inc. Heat sealable films and articles made therefrom
IT1262934B (it) 1992-01-31 1996-07-22 Montecatini Tecnologie Srl Componenti e catalizzatori per la polimerizzazione di olefine
TW294669B (de) * 1992-06-27 1997-01-01 Hoechst Ag
ES2096949T3 (es) 1992-10-02 1997-03-16 Du Pont Pelicula retractil mejorada y procedimientos relacionados con la misma.
US5372980A (en) 1993-06-03 1994-12-13 Polysar Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene-alpha olefin and ethylene-alpha olefin-non-conjugated diolefin elastomers
US5350807A (en) * 1993-06-25 1994-09-27 Phillips Petroleum Company Ethylene polymers
AU692192B2 (en) 1993-10-21 1998-06-04 Mobil Oil Corporation Improved in situ resins of bimodal molecular weight distribution
CA2176387A1 (en) 1993-11-12 1995-05-18 James Mcleod Farley Heat sealable films and articles made therefrom
FI945959A (fi) 1993-12-21 1995-06-22 Hoechst Ag Metalloseenejä ja niiden käyttö katalyytteinä
FI945958A (fi) * 1993-12-21 1995-06-22 Hoechst Ag Menetelmä polyolefiinien valmistamiseksi
JPH09511273A (ja) 1994-03-31 1997-11-11 モービル・オイル・コーポレーション Ｌｌｄｐｅ樹脂ブレンド
IT1269837B (it) 1994-05-26 1997-04-15 Spherilene Srl Componenti e catalizzatori per la polimerizzazione delle olefine
DE69514661T2 (de) 1994-06-24 2000-08-03 Exxon Chemical Patents, Inc. Polymerisationskatalysatorsystem, ihre herstellung und gebrauch
DE19515678B4 (de) * 1995-04-28 2007-12-27 Basell Polyolefine Gmbh Rohr aus Polyethylen mit verbesserten mechanischen Eigenschaften
UA47394C2 (uk) 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Етиленовий полімер, який має підвищену придатність до обробки та вирiб, що містить етиленовий полімер
US5882750A (en) 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
DE19526340A1 (de) * 1995-07-19 1997-01-23 Basf Ag Polyethylenformmassen geringer Schwindungsneigung
IT1275573B (it) 1995-07-20 1997-08-07 Spherilene Spa Processo ed apparecchiatura per la pomimerizzazione in fase gas delle alfa-olefine
JPH0964758A (ja) 1995-08-30 1997-03-07 Matsushita Electric Ind Co Ltd ディジタル携帯無線機の送信装置とそれに用いる高周波電力増幅装置
US5786732A (en) * 1995-10-24 1998-07-28 Vlsi Technology, Inc. Phase locked loop circuitry including a multiple frequency output voltage controlled oscillator circuit
JP2000507499A (ja) 1996-03-29 2000-06-20 ザ・ダウ・ケミカル・カンパニー メタロセン用共触媒
US5942367A (en) 1996-04-24 1999-08-24 Shin-Etsu Chemical Co., Ltd. Chemically amplified positive resist composition, pattern forming method, and method for preparing polymer having a crosslinking group
DE69704614T2 (de) 1996-06-17 2001-11-08 Exxonmobil Chemical Patents Inc., Baytown Olefinpolymerisationkatalysatorsysteme von gemischten übergangsmetalen
CA2259582A1 (en) 1996-07-23 1998-01-29 Stephan James Mclain Polymerization processes for olefins
WO1998004570A1 (de) 1996-07-30 1998-02-05 Studiengesellschaft Kohle Mbh Organochrom-verbindungen enthaltende katalysatoren und ihre verwendung in der alkenpolymerisation
DE19710615A1 (de) 1997-03-14 1998-09-17 Studiengesellschaft Kohle Mbh Organochrom-Verbindungen enthaltende Katalysatoren und ihre Verwendung in der Alkenpolymerisation
WO1998022486A1 (en) 1996-11-15 1998-05-28 Montell Technology Company B.V. Heterocyclic metallocenes and polymerization catalysts
US6423848B2 (en) 1996-12-17 2002-07-23 E. I. Du Pont De Nemours And Company Tridentate ligand
IL129929A0 (en) 1996-12-17 2000-02-29 Du Pont Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis (imines) and novel complexes of pyridinebis(imines) with iron and cobalt
US6432862B1 (en) 1996-12-17 2002-08-13 E. I. Du Pont De Nemours And Company Cobalt catalysts for the polymerization of olefins
US6407192B1 (en) 1997-02-07 2002-06-18 Fina Research, S.A. Production of polyethylene for blow molding
DE19707236A1 (de) 1997-02-24 1998-08-27 Targor Gmbh Katalysatorzusammensetzung
DE19757563A1 (de) 1997-03-07 1999-07-08 Targor Gmbh Geträgertes Katalysatorsystem, Verfahren zur Herstellung und seine Verwendung zur Polymerisation von Olefinen
WO1998040419A1 (de) 1997-03-07 1998-09-17 Targor Gmbh Verfahren zur herstellung von olefinpolymerisaten mit erhöhtem schmelzpunkt
AU6401098A (en) 1997-03-07 1998-09-29 Targor Gmbh Preparation of preparing substituted indanones
US6410664B1 (en) * 1997-03-24 2002-06-25 Cryovac, Inc. Catalyst compositions and processes for olefin polymers and copolymers
DE19733017A1 (de) * 1997-07-31 1999-02-04 Hoechst Ag Chemische Verbindung
PT1015501E (pt) * 1997-09-05 2002-11-29 Bp Chem Int Ltd Catalisadores de polimerizacao
US6462155B1 (en) 1998-02-12 2002-10-08 Idemitsu Petrochemical Co., Ltd. Catalyst for olefin polymerization and process for producing olefin polymer with the catalyst
CA2586497A1 (en) * 1998-03-12 1999-09-16 Ineos Europe Limited Polymerisation catalysts comprising a pyridine-bis(imine) complex
DZ2739A1 (fr) 1998-03-12 2003-09-01 Bp Chem Int Ltd Composition de polyéthylène.
BR9908406B1 (pt) * 1998-03-30 2009-01-13 processo para a polimerizaÇço de olefinas, componente de catalisador de polimerizaÇço e poliolefina.
US7906451B2 (en) * 1998-03-30 2011-03-15 E.I. Du Pont De Nemours And Company Mixed polymerization catalyst component for polymerizing olefins
FI981034A (fi) 1998-05-08 1999-11-09 Borealis Polymers Oy HD-polyeteenikoostumukset ja menetelmä niiden valmistamiseksi
DE19828271A1 (de) 1998-06-25 1999-12-30 Elenac Gmbh Verfahren zur Herstellung eines geträgerten Katalysatorsystems
DE19833170A1 (de) * 1998-07-23 2000-01-27 Targor Gmbh Verfahren zur Herstellung eines metallhaltigen Trägerkatalysators oder einer Trägerkatalysatorkomponente durch Tränkung einer Trägersubstanz
JP3619025B2 (ja) * 1998-09-18 2005-02-09 キヤノン株式会社 符号化方法及び符号化装置
WO2000020427A1 (en) 1998-10-02 2000-04-13 Bp Chemicals Limited Polymerisation catalysts
US6812182B2 (en) 1998-10-23 2004-11-02 Albemarle Corporation Compositions formed from hydroxyaluminoxane and their use as catalyst components
US6160145A (en) 1998-10-23 2000-12-12 Albemarle Corporation Transition metal compounds having conjugate aluminoxate anions and their use as catalyst components
US6492292B2 (en) 1998-10-23 2002-12-10 Albemarle Corporation Gelatinous compositions formed from hydroxyaluminoxane, solid compositions formed therefrom, and the use of such compositions as catalyst components
BR9906934B1 (pt) 1998-11-25 2010-08-24 composto, catalisador, processo para preparar uma poliolefina, e, uso de um catalisador.
EP1133504B1 (de) 1998-11-25 2003-03-12 Basell Polyolefine GmbH Verfahren zur herstellung von monoaryloxy-ansa-metallocenen
DE19858016A1 (de) 1998-12-16 2000-06-21 Basf Ag Neue Metallocenkomplexe
JP2000191719A (ja) * 1998-12-28 2000-07-11 Mitsui Chemicals Inc オレフィン重合用触媒並びにオレフィンの重合方法
GB9906296D0 (en) 1999-03-18 1999-05-12 Bp Chem Int Ltd Polymerisation catalysts
CN1128336C (zh) * 1999-04-02 2003-11-19 富准精密工业(深圳)有限公司 散热器及其制造方法
US6339134B1 (en) * 1999-05-06 2002-01-15 Univation Technologies, Llc Polymerization process for producing easier processing polymers
US6365690B1 (en) 1999-05-06 2002-04-02 E. I. Du Pont De Nemours And Company Polymerization of ethylene
GB9911934D0 (en) 1999-05-21 1999-07-21 Borealis As Polymer
DE19935592A1 (de) 1999-08-02 2001-02-08 Elenac Gmbh Imidochromverbindungen in Katalysatorsystemen für die Olefinpolymerisation
US6919412B1 (en) * 1999-08-13 2005-07-19 Basell Polyolefine Gmbh Monocyclopentadienyl complexes of chromium, molybdenum or tungsten with a donor bridge
US6437161B1 (en) * 1999-08-13 2002-08-20 Basf Aktiengesellschaft Monocyclopentadienyl complexes of chromium, molybdenum or tungsten
JP2003510427A (ja) * 1999-09-29 2003-03-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリエチレンの製造
CA2285723C (en) * 1999-10-07 2009-09-15 Nova Chemicals Corporation Multimodal polyolefin pipe
US6548442B1 (en) 1999-12-03 2003-04-15 Phillips Petroleum Company Organometal compound catalyst
DE19960123A1 (de) * 1999-12-13 2001-06-21 Basf Ag Verfahren zur homogenkatalytischen Herstellung von hochverzweigten amorphen Polyolefinen
JP2001192405A (ja) * 2000-01-12 2001-07-17 Idemitsu Petrochem Co Ltd エチレン単独重合体の製造方法
SG124236A1 (en) 2000-03-30 2006-08-30 Sumitomo Chemical Co Prepolymerization catalyst for use in gas phase polymerization of olefins and process for producing the same
GC0000291A (en) 2000-06-30 2006-11-01 Shell Int Research Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US6444906B1 (en) 2000-08-05 2002-09-03 Charles Marion Lewis Exterior wall-mounted accessory outlet unit for a recreational vehicle, motor home, travel trailer or mobile home
US6900153B2 (en) 2001-03-28 2005-05-31 E.I. Du Pont De Nemours And Company Supported olefin polymerization catalysts
ATE337343T1 (de) * 2001-04-30 2006-09-15 Grace W R & Co Geträgerte dualübergangsmetallkatalysatorsysteme
US6804438B2 (en) 2001-06-29 2004-10-12 Xanoptix, Inc. Method for relaxing mechanical tolerance in an opto-electronic unit
EP1430088B1 (de) 2001-09-14 2008-10-22 Basell Polyolefine GmbH Verfahren zur polymerisation von olefinen
JP2003147009A (ja) * 2001-11-09 2003-05-21 Idemitsu Petrochem Co Ltd オレフィン系重合体の製造方法
AU2003264065A1 (en) * 2002-08-22 2004-03-11 Basell Polyolefine Gmbh Monocyclopentadienyl complexes
EP1403288A1 (de) 2002-09-27 2004-03-31 ATOFINA Research Hafnocenverbindungen enthaltendes Dual-site Katalysatorsystem zur Herstellung von bimodalen Polyolefinen
CN1259347C (zh) 2002-11-07 2006-06-14 中国科学院化学研究所 一种载体化烯烃聚合催化剂及其制备方法
EP1428854A1 (de) 2002-12-09 2004-06-16 Borealis Technology OY Propylen-Polymerzusammensetzungen mit verbessertem Mechanischem und optischem Eigenschaftsprofil
CN101372521B (zh) * 2002-12-20 2011-09-07 巴塞尔聚烯烃有限公司 乙烯和α-烯烃的共聚物
US7730014B2 (en) 2003-03-25 2010-06-01 Hartenstein Mark A Systems and methods for managing affiliations
DE10317395A1 (de) 2003-04-15 2004-11-04 Basell Polyolefine Gmbh Katalysatorsysteme vom Typ der Ziegler-Natta-Katalysatoren und ein Verfahren zu deren Herstellung
TW200504093A (en) 2003-05-12 2005-02-01 Dow Global Technologies Inc Polymer composition and process to manufacture high molecular weight-high density polyethylene and film therefrom
DE10358082A1 (de) 2003-12-10 2005-07-14 Basell Polyolefine Gmbh Organübergangsmetallverbindung, Bscyclopentadienyligandsystem, Katalysatorsystem und Hertellung von Polyolefinen
EP1568716A1 (de) 2004-02-24 2005-08-31 Stichting Dutch Polymer Institute Magnesium Chloride-enthaltendes Katalysatorsystem
ES2299015T3 (es) 2004-03-24 2008-05-16 Shell Internationale Research Maatschappij B.V. Complejos de metales de transicion.
DE102004017093B4 (de) * 2004-04-07 2007-09-20 Leonhard Kurz Gmbh & Co. Kg Prägefolie zur Herstellung fälschungssicherer Kraftfahrzeug-Nummernschilder und fälschungssicheres Kraftfahrzeug-Nummernschild mit einer solchen Prägefolie sowie Verwendung
US7674910B2 (en) 2004-04-08 2010-03-09 Basell Polyolefine Gmbh Process for preparing diimine compounds
DE102004020525A1 (de) * 2004-04-26 2005-11-10 Basell Polyolefine Gmbh Katalysatorsystem zur Olefinpolymerisation, dessen Herstellung und Verwendung
DE102004020524A1 (de) 2004-04-26 2005-11-10 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung zu dessen Herstellung
US7696280B2 (en) 2004-04-30 2010-04-13 Chevron Phillips Chemical Company, Lp HDPE resins for use in pressure pipe and related applications
DE102004029465A1 (de) 2004-06-18 2006-01-05 Basell Polyolefine Gmbh Verfahren zur Bestimmung und Regelung der Zusammensetzung von Polymermischungen bei der Polymerisation
EP1650230A1 (de) 2004-10-21 2006-04-26 Total Petrochemicals Research Feluy Polyolefine hergestellt durch Ziegler -Natta und Metallocene Katalysator in einem einzigen Reaktor
DE102005009916A1 (de) 2005-03-01 2006-09-07 Basell Polyolefine Gmbh Polyethylen Formmasse zum Herstellen von Blasfolien mit verbesserten mechanischen Eigenschaften
DE102005009895A1 (de) 2005-03-01 2006-09-07 Basell Polyolefine Gmbh Polyethylen Formmasse zum Herstellen von Blasfolien mit verbesserten mechanischen Eigenschaften
DE102005009896A1 (de) 2005-03-01 2006-09-07 Basell Polyolefine Gmbh Polyethylen Formmasse zum Herstellen von Blasfolien mit verbesserten mechanischen Eigenschaften
CN100372609C (zh) 2005-04-22 2008-03-05 中国科学院化学研究所 一种用于乙烯齐聚和聚合的催化剂及制备方法和用途
DE102005019393A1 (de) 2005-04-25 2006-10-26 Basell Polyolefine Gmbh Polyethylenformmassen für Spritzgussanwendungen
US7723448B2 (en) 2005-10-14 2010-05-25 Basell Polyolefine Gmbh Hybrid catalyst systems supported on magnesium halide
DE102006001959A1 (de) 2006-01-13 2007-07-19 Basell Polyolefine Gmbh Verfahren zur Herstellung von unsymmetrischen Bis(imino)verbindungen
DE102006022255A1 (de) 2006-05-11 2007-11-15 Basell Polyolefine Gmbh Antistatikum für die Olefinpolymerisation und Verfahren zu dessen Herstellung
US7795411B2 (en) 2006-10-05 2010-09-14 Fred Hutchinson Cancer Research Center Vectors for expressing in vivo biotinylated recombinant proteins
EP2102282B1 (de) 2006-12-22 2011-02-09 Basell Polyolefine GmbH Multimodale polyethylenzusammensetzung, mischkatalysaotr und verfahren zur herstellung der zusammensetzung
JP5462634B2 (ja) 2007-03-06 2014-04-02 バーゼル・ポリオレフィン・ゲーエムベーハー 鉄コンプレックス及び重合プロセスにおけるそれらの使用
DE102007017903A1 (de) 2007-04-13 2008-10-16 Basell Polyolefine Gmbh Polyethylen und Katalysatorzusammensetzung und Verfahren zu dessen Herstellung
US9757585B2 (en) * 2007-06-05 2017-09-12 P Tech, Llc Magnetic joint implant
WO2009080237A1 (en) 2007-12-21 2009-07-02 Basell Polyolefine Gmbh Catalyst sytem for olefin polymerization comprising phenantroline-comprising iron complexes
CN101903418A (zh) 2007-12-21 2010-12-01 巴塞尔聚烯烃股份有限公司 包含菲咯啉的络合物
CN102257014B (zh) 2008-12-17 2014-06-04 巴塞尔聚烯烃股份有限公司 用于烯烃聚合的催化剂体系、它的生产和用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005103095A1 *

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